Synthesis of nanocrystals with exposed high-energy facets is a well-known challenge in many fields of science and technology. The higher reactivity of these facets simultaneously makes them desirable catalysts for sluggish chemical reactions and leads to their small populations in an equilibrated crystal. Using anatase TiO 2 as an example, we demonstrate a facile approach for creating high surface area, stable nanosheets comprised of nearly 100% exposed (001) facets. Our approach relies on spontaneous assembly of the nanosheets into three-dimensional, hierarchical spheres that stabilizes them from collapse. We show that the high surface density of exposed TiO 2 (001) facets leads to fast lithium insertion/deinsertion processes in batteries that mimic features seen in high power electrochemical capacitors.2
Yolk/shell or 'rattle-typed' nanomaterials with nanoparticle cores inside hollow shells are interesting among the complex hollow nanostructures. Yolk/shell nanoparticles (YSNs) are promising functional nanomaterials for a variety of applications such as catalysis, delivery, lithium-ion batteries and biosensors due to their tailorability and functionality in both the cores and hollow shells. This feature article provides an overview of advances in this exciting area of YSNs, covering systematic synthesis approaches and key promising applications based on the literature and our own recent work. We present some strategies for the synthesis of YSNs with controllable sizes, compositions, geometries, structures and functionalities. Applications of these new materials in a wide range of potential areas are discussed including nanoreactors, biomedicine and lithium-ion batteries. Promising future directions of this active research field are also highlighted.
The search for new electrode materials for lithium-ion batteries (LIBs) has been an important way to satisfy the ever-growing demands for better performance with higher energy/power densities, improved safety and longer cycle life. Nanostructured metal oxides exhibit good electrochemical properties, and they are regarded as promising anode materials for high-performance LIBs. In this feature article, we will focus on three different categories of metal oxides with distinct lithium storage mechanisms: tin dioxide (SnO(2)), which utilizes alloying/dealloying processes to reversibly store/release lithium ions during charge/discharge; titanium dioxide (TiO(2)), where lithium ions are inserted/deinserted into/out of the TiO(2) crystal framework; and transition metal oxides including iron oxide and cobalt oxide, which react with lithium ions via an unusual conversion reaction. For all three systems, we will emphasize that creating nanomaterials with unique structures could effectively improve the lithium storage properties of these metal oxides. We will also highlight that the lithium storage capability can be further enhanced through designing advanced nanocomposite materials containing metal oxides and other carbonaceous supports. By providing such a rather systematic survey, we aim to stress the importance of proper nanostructuring and advanced compositing that would result in improved physicochemical properties of metal oxides, thus making them promising negative electrodes for next-generation LIBs.
We report the largely improved electrochemical capacitance of polypyrrole-derived microporous carbon nanospheres (MCNs, 80-100 nm in diameter) containing nitrogen functional groups. We have investigated the electrochemical properties of precursor polypyrrole nanospheres (PNs, with a high N/ C ratio and low surface area) and as-derived carbon nanospheres (CNs, with a moderate N/C ratio and low surface area) prepared by carbonizing PNs at different temperatures, and MCNs (with a low N/C ratio and high surface area) obtained by chemical activation of CNs. The samples are thoroughly characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, thermogravimetric analysis (TGA), nitrogen sorption, elemental analysis, and X-ray photoelectron spectroscopy (XPS). It is found that MCNs with a high surface area and N-doping species exhibit much better capacitive performance compared to the PNs and CNs, and commercial carbon blacks (XC-72 and BP2000) as well. The MCN sample gives a reversible specific capacitance of $240 F g À1 for 3000 cycles in aqueous media as a result of combined advantages of high electrochemical activity of doped heteroatoms (N and O) and accessible well-developed porosity, demonstrating the promising use in high-energy-density supercapacitors.
α-Fe(2)O(3) hollow spheres with sheet-like subunits are synthesized by a facile quasiemulsion-templated method. Glycerol is dispersed in water to form oil-in-water quasiemulsion microdroplets, which serve as soft templates for the deposition of the α-Fe(2)O(3) shell. When tested as anode materials for lithium-ion batteries, these α-Fe(2)O(3) hollow spheres manifest greatly enhanced Li storage properties.
The development of new electrode materials for lithium-ion batteries (LIBs) has always been a focal area of materials science, as the current technology may not be able to meet the high energy demands for electronic devices with better performance. Among all the metal oxides, tin dioxide (SnO₂) is regarded as a promising candidate to serve as the anode material for LIBs due to its high theoretical capacity. Here, a thorough survey is provided of the synthesis of SnO₂-based nanomaterials with various structures and chemical compositions, and their application as negative electrodes for LIBs. It covers SnO₂ with different morphologies ranging from 1D nanorods/nanowires/nanotubes, to 2D nanosheets, to 3D hollow nanostructures. Nanocomposites consisting of SnO₂ and different carbonaceous supports, e.g., amorphous carbon, carbon nanotubes, graphene, are also investigated. The use of Sn-based nanomaterials as the anode material for LIBs will be briefly discussed as well. The aim of this review is to provide an in-depth and rational understanding such that the electrochemical properties of SnO₂-based anodes can be effectively enhanced by making proper nanostructures with optimized chemical composition. By focusing on SnO₂, the hope is that such concepts and strategies can be extended to other potential metal oxides, such as titanium dioxide or iron oxides, thus shedding some light on the future development of high-performance metal-oxide based negative electrodes for LIBs.
We report a simple glucose-mediated hydrothermal method for gram-scale synthesis of nearly monodisperse hybrid SnO 2 nanoparticles. Glucose is found to play the dual role of facilitating rapid precipitation of polycrystalline SnO 2 nanocolloids and in creating a uniform, glucose-derived, carbon-rich polysaccharide (GCP) coating on the SnO 2 nanocores. The thickness of the GCP coating can be facilely manipulated by varying glucose concentration in the synthesis medium. Carbon-coated SnO 2 nanocolloids obtained after carbonization of the GCP coating exhibit significantly enhanced cycling performance for lithium storage. Specifically, we find that a capacity of ca. 440 mA h/g can be obtained after more than 100 charge/discharge cycles at a current density of 300 mA/g in hybrid SnO 2 -carbon electrodes containing as much as 1/3 of their mass in the lowactivity carbon shell. By reducing the SnO 2 -carbon particles with H 2 , we demonstrate a simple route to carbon-coated Sn nanospheres. Lithium storage properties of the latter materials are also reported. Our results suggest that large initial irreversible losses in these materials are caused not only by the initial, presumably irreversible, reduction of SnO 2 as generally perceived in the field, but also by the formation of the solid electrolyte interface (SEI).
In this work, a novel hydrothermal route is developed to synthesize cobalt carbonate hydroxide, Co(CO3)0.5(OH)·0.11H2O. In this method, sodium chloride salt is utilized to organize single‐crystalline nanowires into a chrysanthemum‐like hierarchical assembly. The morphological evolution process of this organized product is investigated by examining different reaction intermediates during the synthesis. The growth and thus the final assembly of the Co(CO3)0.5(OH)·0.11H2O can be finely tuned by selecting preparative parameters, such as the molar ratio of the starting chemicals, the additives, the reaction time and the temperature. Using the flower‐like Co(CO3)0.5(OH)·0.11H2O as a solid precursor, quasi‐single‐crystalline mesoporous Co3O4 nanowire arrays are prepared via thermal decomposition in air. Furthermore, carbon can be added onto the spinel oxide by a chemical‐vapor‐deposition method using acetylene, which leads to the generation of carbon‐sheathed CoO nanowire arrays (CoO@C). Through comparing and analyzing the crystal structures, the resultant products and their high crystallinity can be explained by a sequential topotactic transformation of the respective precursors. The electrochemical performances of the typical cobalt oxide products are also evaluated. It is demonstrated that tuning of the surface texture and the pore size of the Co3O4 products is very important in lithium‐ion‐battery applications. The carbon‐decorated CoO nanowire arrays exhibit an excellent cyclic performance with nearly 100% capacity retention in a testing range of 70 cycles. Therefore, this CoO@C nanocomposite can be considered to be an attractive candidate as an anode material for further investigation.
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