Triangular Ni(HCO3)2 nanosheets were synthesized via a template-free solvothermal method. The phase transition and formation mechanism were explored systematically. Further investigation indicated that the reaction time and pH have significant effects on the morphology and size distribution of the triangular Ni(HCO3)2 nanosheets. More interestingly, the resulting product had an ultra-thin structure and high specific surface area, which can effectively accelerate the charge transport during charge–discharge processes. As a result, the triangular Ni(HCO3)2 nanosheets not only exhibited high specific capacitance (1,797 F·g-1 at 5 A·g-1 and 1,060 F·g-1 at 50 A·g-1), but also showed excellent cycling stability with a high current density (~80% capacitance retention after 5,000 cycles at the current density of 20 A·g-1).
Mixed transition metal oxides (MTMOs) have received intensive attention as promising anode materials for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). In this work, we demonstrate a facile one-step water-bath method for the preparation of graphene oxide (GO) decorated Fe2(MoO4)3 (FMO) microflower composite (FMO/GO), in which the FMO is constructed by numerous nanosheets. The resulting FMO/GO exhibits excellent electrochemical performances in both LIBs and SIBs. As the anode material for LIBs, the FMO/GO delivers a high capacity of 1,220 mAh·g–1 at 200 mA·g–1 after 50 cycles and a capacity of 685 mAh·g–1 at a high current density of 10 A·g–1. As the anode material for SIBs, the FMO/GO shows an initial discharge capacity of 571 mAh·g–1 at 100 mA·g–1, maintaining a discharge capacity of 307 mAh·g–1 after 100 cycles. The promising performance is attributed to the good electrical transport from the intimate contact between FMO and graphene oxide. This work indicates that the FMO/GO composite is a promising anode for high-performance lithium and sodium storage.
The construction of metal sulfides-carbon nanocomposites with a hollow structure is highly attractive for various energy storage and conversion technologies. Herein, we report a facile two-step method for preparing a nanocomposite with CoS2 nanoparticles in N-doped carbon nanotube hollow frameworks (NCNTFs). Starting from zeolitic imidazolate framework-67 (ZIF-67) particles, in situ reduced metallic cobalt nanocrystals expedite the formation of the hierarchical hollow frameworks from staggered carbon nanotubes via a carbonization process. After a follow-up sulfidation reaction with sulfur powder, the embedded cobalt crystals are transformed into CoS2 nanoparticles. Benefitting from the robust hollow frameworks made of N-doped carbon nanotubes and highly active CoS2 ultrafine nanoparticles, this advanced nanocomposite shows greatly enhanced lithium storage properties when evaluated as an electrode for lithium-ion batteries. Impressively, the resultant CoS2/NCNTF material delivers a high specific capacity of ～937 mAh·g–1 at a current density of 1.0 A·g–1 with a cycle life longer than 160 cycles.
Herein, hierarchically structured SnO2 microspheres are designed and synthesized as an efficient anode material for lithium-ion batteries using hollow SnO2 nanoplates. Three-dimensionally ordered macroporous (3-DOM) SnOx-C microspheres synthesized by spray pyrolysis are transformed into hierarchically structured SnO2 microspheres by a two-step post-treatment process. Sulfidation produces hierarchically structured SnS-SnS2-C microspheres comprising tin sulfide nanoplate and carbon building blocks. A subsequent oxidation process produces SnO2 microspheres from hollow SnO2 nanoplate building blocks, which are formed by Kirkendall diffusion. The discharge capacity of the hierarchically structured SnO2 microspheres at a current density of 5 A·g?1 for the 600th cycle is 404 mA·h·g?1. The hierarchically structured SnO2 microspheres have reversible discharge capacities of 609 and 158 mA·h·g?1 at current densities of 0.5 and 30 A·g?1, respectively. The ultrafine nanosheets contain empty voids that allow excellent lithium-ion storage performance, even at high current densities.
Scrupulous design and fabrication of advanced electrode materials are vital for developing high-performance sodium ion batteries. Herein, we report a facile one-step hydrothermal strategy for construction of a C-MoSe2/rGO composite with both high porosity and large surface area. Double modification of MoSe2 nanosheets is realized in this composite by introducing a reduced graphene oxide (rGO) skeleton and outer carbon protective layer. The MoSe2 nanosheets are well wrapped by a carbon layer and also strongly anchored on the interconnected rGO network. As an anode in sodium ion batteries, the designed C-MoSe2/rGO composite delivers noticeably enhanced sodium ion storage, with a high specific capacity of 445 mAh·g-1 at 200 mA·g-1 after 350 cycles, and 228 mAh·g-1 even at 4 A·g-1; these values are much better than those of C-MoSe2 nanosheets (258 mAh·g-1 at 200 mA·g-1 and 75 mAh·g-1 at 4 A·g-1). Additionally, the sodium ion storage mechanism is investigated well using ex situ X-ray diffraction and transmission electron microscopy methods. Our proposed electrode design protocol and sodium storage mechanism may pave the way for the fabrication of other high-performance metal diselenide anodes for electrochemical energy storage.
Micro-supercapacitors (MSCs) as important on-chip micropower sources have attracted considerable attention because of their unique and advantageous design for optimized maximum functionality within a minimized sized chip and excellent mechanical flexibility/stability in miniaturized portable electronic device applications. In this work, we report a novel, high-performance flexible integrated on-chip MSC based on hybrid nanostructures of reduced graphene oxide/Fe2O3 hollow nanospheres using a microelectronic photo-lithography technology combined with plasma etching technique. The unique structural design for on-chip MSCs enables high-performance enhancements compared with graphene-only devices, exhibiting high specific capacitances of 11.57 F·cm-3 at a scan rate of 200 mV·s-1 and excellent rate capability and robust cycling stability with capacitance retention of 92.08% after 32,000 charge/discharge cycles. Moreover, the on-chip MSCs exhibit superior flexibility and outstanding stability even after repetition of charge/discharge cycles under different bending states. As-fabricated highly flexible on-chip MSCs can be easily integrated with CdS nanowire-based photodetectors to form a highly compacted photodetecting system, exhibiting comparable performance to devices driven by conventional external energy storage units.
Iron oxides have attracted considerable interest as abundant materials for high-capacity Li-ion battery anodes. However, their fast capacity fading owing to poorly controlled reversibility of the conversion reactions greatly hinders their application. Here, a sandwich-structured nanocomposite of N-doped graphene and nearly monodisperse Fe3O4 nanoparticles were developed as high-performance Li-ion battery anode. N-doped graphene serves as a conducting framework for the self-assembled structure and controls Fe3O4 nucleation through the interaction of N dopants, surfactant molecules, and iron precursors. Fe3O4 nanoparticles were well dispersed with a uniform diameter of ~15 nm. The unique sandwich structure enables good electron conductivity and Li-ion accessibility and accommodates a large volume change. Hence, it delivers good cycling reversibility and rate performance with a capacity of ~1,227 mA·h·g–1 and 96.8% capacity retention over 1,000 cycles at a current density of 3 A·g–1. Our work provides an ideal structure design for conversion anodes or other electrode materials requiring a large volume change.
Nanomaterials with electrochemical activity are always suffering from aggregations, particularly during the high-temperature synthesis processes, which will lead to decreased energy-storage performance. Here, hierarchically structured lithium titanate/nitrogen-doped porous graphene fiber nanocomposites were synthesized by using confined growth of Li4Ti5O12 (LTO) nanoparticles in nitrogen-doped mesoporous graphene fibers (NPGF). NPGFs with uniform pore structure are used as templates for hosting LTO precursors, followed by high-temperature treatment at 800 °C under argon (Ar). LTO nanoparticles with size of several nanometers are successfully synthesized in the mesopores of NPGFs, forming nanostructured LTO/NPGF composite fibers. As an anode material for lithium-ion batteries, such nanocomposite architecture offers effective electron and ion transport, and robust structure. Such nanocomposites in the electrodes delivered a high reversible capacity (164 mAh·g–1 at 0.3 C), excellent rate capability (102 mAh·g–1 at 10 C), and long cycling stability.
The assembly of hybrid nanomaterials has opened up a new direction for the construction of high-performance anodes for lithium-ion batteries (LIBs). In this work, we present a straightforward, eco-friendly, one-step hydrothermal protocol for the synthesis of a new type of Fe2O3-SnO2/graphene hybrid, in which zero-dimensional (0D) SnO2 nanoparticles with an average diameter of 8 nm and one-dimensional (1D) Fe2O3 nanorods with a length of ~150 nm are homogeneously attached onto two-dimensional (2D) reduced graphene oxide nanosheets, generating a unique point-line-plane (0D-1D-2D) architecture. The achieved Fe2O3-SnO2/graphene exhibits a well-defined morphology, a uniform size, and good monodispersity. As anode materials for LIBs, the hybrids exhibit a remarkable reversible capacity of 1,530 mA·g?1 at a current density of 100 mA·g?1 after 200 cycles, as well as a high rate capability of 615 mAh·g?1 at 2,000 mA·g?1. Detailed characterizations reveal that the superior lithium-storage capacity and good cycle stability of the hybrids arise from their peculiar hybrid nanostructure and conductive graphene matrix, as well as the synergistic interaction among the components.
Spinel LiMn2O4 is a widely utilized cathode material for Li-ion batteries. However, its applications are limited by its poor energy density and power density. Herein, a novel hierarchical porous onion-like LiMn2O4(LMO) was prepared to shorten the Li+ diffusion pathway with the presence of uniform pores and nanosized primary particles. The growth mechanism of the porous onion-like LiMn2O4 was analyzed to control the morphology and the crystal structure so that it forms a polyhedral crystal structure with reduced Mn dissolution. In addition, graphene was added to the cathode (LiMn2O4/graphene) to enhance the electronic conductivity. The synthesized LiMn2O4/graphene exhibited an ultrahigh-rate performance of 110.4 mAh·g–1 at 50 C and an outstanding energy density at a high power density, maintaining 379.4 Wh·kg–1 at 25,293 W·kg–1. Besides, it shows durable stability, with only 0.02% decrease in the capacity per cycle at 10 C. Furthermore, the (LiMn2O4/graphene)/graphite full-cell exhibited a high discharge capacity. This work provides a promising method for the preparation of outstanding, integrated cathodes for potential applications in lithium ion batteries.
PX-phase PbTiO3 (PT) nanowires with open channels running along the length direction have been investigated as an anode material for lithium ion batteries. This material shows a stabilized reversible specific capacity of about 410 mAh·g–1 up to 200 cycles with a charge/discharge voltage plateau of around 0.3–0.65 V. In addition, it exhibits superior high-rate performance, with 90% and 77% capacity retention observed at 1 and 2 A·g–1, respectively. At a very high current rate of 10 A·g–1, a specific capacity of over 170 mAh·g–1 is retained up to 100 cycles, significantly outperforming the rate capability reported for Pb and Pb oxides. The results of X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) analyses along with the cyclic voltammogram results reveal that the PX-phase PT nanowires undergo irreversible structural amorphization and reduction reactions during the initial cycle, which allow them to transform into a composite structure composed of 2–5 nm Pb nanoparticles uniformly dispersed in the 1D amorphous Li2O·TiO2·LiTiO2 matrix. In this composite structure, the presence of abundant amounts of Ti3+ in both the charged and discharged states enhances the electrical conductance of the system, whereas the presence of ultrafine Pb nanoparticles imparts high reversible capacity. The structurally stable TiO2-based amorphous matrix can also considerably buffer the volume variation during the charge/discharge process, thereby facilitating extremely stable cycling performance. This compound combines the high specific capacity of Pb-based materials and the good rate capability of Ti3+-based wiring. Our results might furnish a possible route for achieving superior cycling and rate performance and contribute towards the search for next-generation anode materials.
The synthesis of a composite of cobalt phosphide nanowires and reduced graphene oxide (denoted CoP/RGO) via a facile hydrothermal method combined with a subsequent annealing step is reported. The resulting composite presents large specific surface area and enhanced conductivity, which can effectively facilitate charge transport and accommodates variations in volume during the lithiation/de-lithiation processes. As a result, the CoP/RGO nanocomposite manifests a high reversible specific capacity of 960 mA·h·g–1 over 200 cycles at a current density of 0.2 A·g–1 (297 mA·h·g–1 over 10,000 cycles at a current density of 20 A·g–1) and excellent rate capability (424 mA·h·g–1 at a current density of 10 A·g–1).
Because of the coupling between semiconducting and piezoelectric properties in wurtzite materials, strain-induced piezo-charges can tune the charge transport across the interface or junction, which is referred to as the piezotronic effect. For devices whose dimension is much smaller than the mean free path of carriers (such as a single atomic layer of MoS2), ballistic transport occurs. In this study, transport in the monolayer MoS2 piezotronic transistor is studied by presenting analytical solutions for two-dimensional (2D) MoS2. Furthermore, a numerical simulation for guiding future 2D piezotronic nanodevice design is presented.
Conducting polymers generally show high specific capacitance but suffer from poor rate capability and rapid capacitance decay, which greatly limits their practical applications in supercapacitor electrodes. To this end, many studies have focused on improving the overall capacitive performance by synthesizing nanostructured conducting polymers or by depositing a range of coatings to increase the active surface area exposed to the electrolyte and enhance the charge transport efficiency and structural stability. Despite this, simultaneously achieving high specific capacitance, good rate performance, and long cycle life remains a considerable challenge. Among the various two-dimensional (2D) layered materials, octahedral (1T) phase molybdenum disulfide (MoS2) nanosheets have high electrical conductivity, large specific surface areas, and unique surface chemical characteristics, making them an interesting substrate for the controlled growth of nanostructured conducting polymers. This paper reports the rational synthesis of carbon shell-coated polyaniline (PANI) grown on 1T MoS2 monolayers (MoS2/PANI@C). The composite electrode comprised of MoS2/PANI@C with a ~3 nm carbon shell exhibited a remarkable specific capacitance of up to 678 F·g–1 (1 mV·s–1), superior capacity retention of 80% after 10,000 cycles and good rate performance (81% at 10 mV·s–1) due to the multiple synergic effects between the PANI nanostructure and 1T MoS2 substrates as well as protection by the uniform thin carbon shell. These properties are comparable to the best overall capacitive performance achieved for conducting polymers-based supercapacitor electrodes reported thus far.
Rechargeable metal-iodine batteries are an emerging attractive electrochemical energy storage technology that combines metallic anodes with halogen cathodes. Such batteries using aqueous electrolytes represent a viable solution for the safety and cost issues associated with organic electrolytes. A hybrid-electrolyte battery architecture has been adopted in a lithium-iodine battery using a solid ceramic membrane that protects the metallic anode from contacting the aqueous electrolyte. Here we demonstrate an eco-friendly, low-cost zinc-iodine battery with an aqueous electrolyte, wherein active I2 is confined in a nanoporous carbon cloth substrate. The electrochemical reaction is confined in the nanopores as a single conversion reaction, thus avoiding the production of I3? intermediates. The cathode architecture fully utilizes the active I2, showing a capacity of 255 mAh·g?1 and low capacity cycling fading. The battery provides an energy density of ～ 151 Wh·kg?1 and exhibits an ultrastable cycle life of more than 1,500 cycles.
We report the investigation of the thermoelectric properties of large-scale solution-synthesized Bi2Te3 nanocomposites prepared from nanowires hotpressed into bulk pellets. A third element, Se, is introduced to tune the carrier concentration of the nanocomposites. Due to the Se doping, the thermoelectric figure of merit (ZT) of the nanocomposites is significantly enhanced due to the increased power factor and reduced thermal conductivity. We also find that thermal transport in our hot-pressed pellets is anisotropic, which results in different thermal conductivities along the in-plane and cross-plane directions. Theoretical calculations for both electronic and thermal transport are carried out to establish fundamental understanding of the material system and provide directions for further ZT optimization with adjustments to carrier concentration and mobility.
We have demonstrated the improved performance of oxygen evolution reactions (OER) using Au/nickel phosphide (Ni12P5) core/shell nanoparticles (NPs) under basic conditions. NPs with a Ni12P5 shell and a Au core, both of which have well-defined crystal structures, have been prepared using solution-based synthetic routes. Compared with pure Ni12P5 NPs and Au-Ni12P5 oligomer-like NPs, the core/shell crystalline structure with Au shows an improved OER activity. It affords a current density of 10 mA/cm2 at a small overpotential of 0.34 V, in 1 M KOH aqueous solution at room temperature. This enhanced OER activity may relate to the strong structural and effective electronic coupling between the single-crystal core and the shell.
Hollow nanostructures have attracted considerable attention owing to their large surface area, tunable cavity, and low density. In this study, a unique flower-like C@SnOX@C hollow nanostructure (denoted as C@SnOX@C-1) was synthesized through a novel one-pot approach. The C@SnOX@C-1 had a hollow carbon core and interlaced petals on the shell. Each petal was a SnO2 nanosheet coated with an ultrathin carbon layer ~2 nm thick. The generation of the hollow carbon core, the growth of the SnO2 nanosheets, and the coating of the carbon layers were simultaneously completed via a hydrothermal process using resorcinol-formaldehyde resin-coated SiO2 nanospheres, tin chloride, urea, and glucose as precursors. The resultant architecture with a large surface area exhibited excellent lithium-storage performance, delivering a high reversible capacity of 756.9 mA·h·g–1 at a current density of 100 mA·g–1 after 100 cycles.
Hexagonal ultrathin WO3 nano-ribbons (HUWNRs) of subnanometer thicknesses, 2–5 nm widths, and lengths of up to several micrometers were prepared by a solvothermal method. The as-prepared HUWNRs grow along the [001] direction, and the main exposed facet is the (120) crystal plane. The HUWNRs exhibit good electrochemical performance as an anode material in lithium ion batteries because of their unique structure. It is believed that these unique materials may be applied in many fields.
Electrical and optical enhancements of single-layer semiconducting materials such as transition metal dichalcogenides have recently been studied to achieve sensitive properties via external treatments, such as the formation of organic/inorganic protecting layers on field-effect transistors (FETs), thermal annealing, and nano-dot doping of sensors and detectors. Here, we propose a new analytical approach to electrical and optical enhancement through a passivation process using atomic layer deposition (ALD), and demonstrate a synthesized MoS2 monolayer incorporated with Al atoms in an Al2O3 passivation layer. The incorporated Al atoms in the MoS2 monolayer are clearly observed by spherical aberration-corrected scanning transmission electron microscopy (Cs-STEM) and TEM-energy-dispersive X-ray spectroscopy results. We demonstrate that the chemically incorporated FETs exhibit highly enhanced mobilities of approximately 3.7 cm2·V?1·s?1, forty times greater than that of as-synthesized MoS2, with a three-fold improvement in the photoluminescence properties.
