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.
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).
Sodium-ion batteries (SIBs) have been increasingly attracting attention as a sustainable alternative to lithium-ion batteries for scalable energy storage. The key to advanced SIBs relies heavily upon the development of reliable anodes. In this respect, Bi2S3 has been extensively investigated because of its high capacity, tailorable morphology, and low cost. However, the common practices of incorporating carbon species to enhance the electrical conductivity and accommodate the volume change of Bi2S3 anodes so as to boost their durability for Na storage have met with limited success. Herein, we report a simple method to realize the encapsulation of Bi2S3 nanorods within three-dimensional, nitrogen-doped graphene (3DNG) frameworks, targeting flexible and active composite anodes for SIBs. The Bi2S3/3DNG composites displayed outstanding Na storage behavior with a high reversible capacity (649 mAh·g–1 at 62.5 mA·g–1) and favorable durability (307 and 200 mAh·g–1 after 100 cycles at 125 and 312.5 mA·g–1, respectively). In-depth characterization by in situ X-ray diffraction revealed that the intriguing Na storage process of Bi2S3 was based upon a reversible reaction. Furthermore, a full, flexible SIB cell with Na0.4MnO2 cathode and as-prepared composite anode was successfully assembled, and holds a great promise for next-generation, wearable energy storage applications.
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.
T-Nb2O5/reduced graphene oxide nanohybrids were fabricated via the hydrothermal attachment of Nb2O5 nanowires to dispersed graphene oxide nanosheets followed by a high-temperature phase transformation. Electrochemical measurements showed that the nanohybrid anodes possessed enhanced reversible capacity and superior cycling stability compared to those of a pristine T-Nb2O5 nanowire electrode. Owing to the strong bonds between graphene nanosheets and T-Nb2O5 nanowires, the nanohybrids achieved an initial capacity of 227 mAh·g?1. Additionally, non-aqueous asymmetric supercapacitors (ASCs) were fabricated with the synthesized nanohybrids as the anode and activated carbon as the cathode. The 3 V Li-ion ASC with a LiPF6-based organic electrolyte achieved an energy density of 45.1 Wh·kg?1 at 715.2 W·kg?1. The working potential could be further enhanced to 4 V when a polymer ionogel separator (PVDF-HFP/LiTFSI/EMIMBF4) and formulated ionic liquid electrolyte were employed. Such a quasi-solid state ASC could operate at 60 °C and delivered a maximum energy density of 70 Wh·kg?1 at 1 kW·kg?1.
Silicon is considered an exceptionally promising alternative to the most commonly used material, graphite, as an anode for next-generation lithium-ion batteries, as it has high energy density owing to its high theoretical capacity and abundant storage. Here, microsized walnut-like porous silicon/reduced graphene oxide (P-Si/rGO) core–shell composites are successfully prepared via in situ reduction followed by a dealloying process. The composites show specific capacities of more than 2,100 mAh·g?1 at a current density of 1,000 mA·g?1, 1,600 mAh·g?1 at 2,000 mA·g?1, 1,500 mAh·g?1 at 3,000 mA·g?1, 1,200 mAh·g?1 at 4,000 mA·g?1, and 950 mAh·g?1 at 5,000 mA·g?1, and maintain a value of 1,258 mAh·g?1 after 300 cycles at a current density of 1,000 mA·g?1. Their excellent rate performance and cycling stability can be attributed to the unique structural design: 1) The graphene shell dramatically improves the conductivity and stabilizes the solid–electrolyte interface layers; 2) the inner porous structure supplies sufficient space for silicon expansion; 3) the nanostructure of silicon can prevent the pulverization resulting from volume expansion stress. Notably, this in situ reduction method can be applied as a universal formula to coat graphene on almost all types of metals and alloys of various sizes, shapes, and compositions without adding any reagents to afford energy storage materials, graphene-based catalytic materials, graphene-enhanced composites, etc.
Developments of nanostructured transition metal dichalcogenides (TMDs) materials as novel electrocatalyst candidates for oxygen reduction reaction (ORR) is a new strategy to promote the developments of non-precious metal ORR catalysts. In this work, a three-dimensional (3D) hybrid of rosebud-like MoSe2 nanostructures supported on reduced graphene oxide (rGO) nanosheets was successfully synthesized through a facile hydrothermal strategy. The prepared MoSe2@rGO hybrid nanostructure showed enhanced electrocatalytic activity for the ORR in alkaline medium compared to that of the pure MoSe2, rGO, and their simple physical mixture, which could benefit from the excellent oxygen adsorption ability of the abundantly exposed active edge sites of the ultrathin MoSe2 layers, the conductivity and aggregation-limiting effect of the rGO platform, as well as the unique 3D rosebud-like architecture of the hybrid material. The electrocatalytic activity of the MoSe2@rGO hybrid towards ORR was comparable to that of commercial Pt/C catalysts. And the promoted reaction was revealed to involve a nearly four-electron-dominated ORR process by analysis of the obtained Koutecky–Levich plots. The scanning electrochemical microscopy (SECM) technique, with the advantages of investigating of the local catalytic activity of samples with high spatial resolution and simultaneously evaluating activities of different catalysts in a single experiment, was further applied to investigate the local ORR electrocatalytic activity of MoSe2@rGO and compare it with those of other catalyst samples through applying different sample potentials. The excellent stability and methanol tolerance of the 3D nanostructured MoSe2@rGO hybrid against methanol further prove the 3D nanostructured MoSe2@rGO hybrid as a promising ORR electrocatalyst in alkaline solution for potential applications in fuel cells and metal–air batteries.
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.
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.
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.
We report the synthesis and electrochemical sodium storage of cobalt disulfide (CoS2) with various micro/nano-structures. CoS2 with microscale sizes are either assembled by nanoparticles (P-CoS2) via a facile solvothermal route or nanooctahedrons constructed solid (O-CoS2) and hollow microstructures (H-CoS2) fabricated by hydrothermal methods. Among three morphologies, H-CoS2 exhibits the largest discharge capacities and best rate performance as anode of sodium-ion batteries (SIBs). Furthermore, H-CoS2 delivers a capacity of 690 mA·h·g?1 at 1 A·g?1 after 100 cycles in a potential range of 0.1–3.0 V, and ～240 mA·h·g?1 over 800 cycles in the potential window of 1.0–3.0 V. This cycling difference mainly lies in the two discharge plateaus observed in 0.1–3.0 V and one discharge plateau in 1.0–3.0 V. To interpret the reactions, X-ray diffraction (XRD) and transmission electron microscopy (TEM) are applied. The results show that at the first plateau around 1.4 V, the insertion reaction (CoS2 + xNa+ + xe? → NaxCoS2) occurs; while at the second plateau around 0.6 V, the conversion reaction (NaxCoS2 + (4 ? x) Na+ + (4 ? x)e? → Co + 2Na2S) takes place. This provides insights for electrochemical sodium storage of CoS2 as the anode of SIBs.
We report the facile, one-pot synthesis of 3-D urchin-like W18O49 nanostructures (U-WO) via a simple solvothermal approach. An excellent supercapacitive performance was achieved by the U-WO because of its large Brunauer–Emmett–Teller (BET) specific surface area (ca. 123 m2·g–1) and unique morphological and structural features. The U-WO electrodes not only exhibit a high rate-capability with a specific capacitance (Csp) of ~235 F·g–1 at a current density of 20 A·g–1, but also superior long-life performance for 1,000 cycles, and even up to 7,000 cycles, showing ~176 F·g–1 at a high current density of 40 A·g–1.
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.
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.
In recent years, development of all-solid-state batteries has become a promising approach to improve the safety of batteries. Herein, we report the preparation of a new composite polymer electrolyte (CPE) for use in all-solid-state sodium ion batteries. The CPE comprising of poly(methacrylate) (PMA), poly(ethylene glycol) (PEG), α-Al2O3 with acidic surface sites, and NaClO4 exhibited high ionic conductivity (1.46 × 10-4 S·cm-1 at 70 °C), wide electrochemical stability window (4.5 V vs. Na+/Na), and good mechanical strength. With the introduction of the prepared CPE and Na3V2(PO4)3, the final all-solid-state sodium ion batteries showed good rate and cycle performance, with a high reversible capacity of 85 mAh·g-1 when operated at 0.5 C (1 C = 118 mA·g–1) and 94.1% capacity retention rate after 350 cycles at 70 °C. Our work provides a novel solid electrolyte for the development of all-solid-state sodium 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.
Germanium-based oxide has been found to be a promising high-capacity anode material for lithium-ion batteries (LIBs). However, it exhibits poor electrochemical performance because of the drastic volume change during cycling. Herein, we designed porous Ge-Fe bimetal oxide nanowires (Ge-Fe-Ox-700 NWs) by a large-scale and facile solvothermal reaction. When used as the anode material for LIBs, these Ge-Fe-Ox-700 NWs exhibited superior electrochemical performance (～ 1,120 mAh·g?1 at a current density of 100 mA·g?1) and good cycling performance (～ 750 mAh·g?1 after 50 cycles at a current density of 100 mA·g?1). The improved performance is due to the small NW diameter, which allows for better accommodation of the drastic volume changes and zero-dimensional nanoparticles, which shorten the diffusion length of ions and electrons.
Sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) have been considered as attractive alternatives for next-generation battery systems, which have promising application potential due to their earth abundance of potassium and sodium, high capacity and suitable working potential, however, the design and application of bi-functional high-performance anode still remain a great challenge up to date. Bismuth sulfide is suitable as anode owing to its unique laminar structure with relatively large interlayer distance to accommodate larger radius ions, high theoretical capacity and high volumetric capacity etc. In this study, dandelion-like Bi2S3/rGO hierarchical microspheres as anode material for PIBs displayed reversible capacity, and 206.91 mAh·g−1 could be remained after 1,200 cycles at a current density of 100 mA·g−1. When applied as anode materials for SIBs, 300 mAh·g−1 could be retained after 300 cycles at 2 A·g−1 and its initial Coulombic efficiency is as high as 97.43%. Even at high current density of 10 A·g−1, 120.3 mAh·g−1 could be preserved after 3,400 cycles. The Na3V2(PO4)3@rGO//Bi2S3/rGO sodium ion full cells were successfully assembled which displays stable performance after 60 cycles at 100 mA·g−1. The above results demonstrate that Bi2S3/rGO has application potential as high performance bi-functional anode for PIBs and SIBs.
Few-layered MoSe2 nanosheets with mixed 1T/2H phase were successfully arrayed on a Ti substrate (forming 1T@2H-MoSe2/Ti) through a facile one-step solvothermal process. After testing different synthesis conditions, it was found that the optimal process involves a temperature of 200 °C and a reaction time of 12 h. Structural characterizations reveal that the morphology of 1T@2H-MoSe2 consists of edge-terminated nanosheets with one to five layers, composed of a mixed 1T/2H phase dominated by the 1T one. The 1T@2H-MoSe2/Ti electrode shows excellent HER catalytic activity, with a small onset potential (?120 mV vs. reversible hydrogen electrode, RHE) and an electrode potential of only ?133 mV (vs. RHE) to achieve a current density of 20 mA·cm?2. This excellent electrocatalytic activity is due to the synergistic effects of 1T metallic phase, few-layered nanosheet morphology, and direct growth of 1T@2H-MoSe2on the Ti substrate. In addition, the 1T@2H-MoSe2/Ti electrode shows excellent stability towards long-term electrolysis. This is due to the long-term stability of the valence states of Mo and Se, as shown by post-electrolysis X-ray photoelectron spectroscopy analysis.
