The optimized growth conditions for high density germanium（Ge） nanowires and P-doped Ge nanowires on Si（111） substrate were investigated,the phosphorus（P）-doping in Ge nanowires was also characterized.Vapor liquid solid-low pressure chemical vapor deposition（VLS-LPCVD） of Ge nanowires was conducted with different thicknesses of Au film as catalyst,different flow rates of GeH4 as precursor and PH3/Ar as co-flow.The morphologies of the Ge nanowires were characterized by scanning electron microscopy（SEM）,the P-doping was verified by micro Raman spectroscopy via measuring the P local vibrational peak（342-345 cm^（-1）） and asymmetric broadening of Ge-Ge vibrational peak（about 300 cm^（-1）,respectively.The characterization results show that 1 run thickness of Au catalyst is the most suitable condition among thicknesses of 0.1,1,5,and 10 nm for the growth of high density Ge nanowires at 300 and 350℃,and 0.5 sccm is the best flow rate of PH3/Ar to grow high density and large scale P-doped Ge nanowires among flow rates of 0.5,1 and 2sccm.The P impurity can be doped into Ge nanowires effectively during LPCVD process at 350 ℃.
Lithium nickel manganese oxide spinel(Li Ni0.5-Mn1.5O4, LNMO) has attracted much attention as the cathode material for rechargeable lithium-ion batteries due to its high energy density and low cost. However, the short cycle life and poor high-rate capability hinder its commercialization. In this study, we synthesized hollow spherical LNMO built from polyhedral particles. The LNMO hollow structure guarantees sufficient contact with electrolyte and rapid diffusion of lithium ions. To enhance the conductivity, we use carbon nanotubes(CNTs) to modify the surface of the cathode. After CNT modification, the LNMO hollow structure manifests outstanding cycling stability and high-rate capability. It delivers a discharge capacity of 127 m A h g-1 at 5 C, maintaining 104 m A h g-1 after 500 cycles. Even at a high rate of 20 C, a capacity of 121 m A h g-1 can be obtained. The excellent electrochemical performance is ascribed to the unique structure and the enhanced conductivity through CNT modification. It is demonstrated that the CNTmodified hollow spherical LNMO is a promising cathode for lithium ion batteries.
Naturally abundant transition metal oxides with high theoretical capacity have attracted more attention than commercial graphite for use as anodes in lithium-ion batteries. Lithium-ion battery electrodes that exhibit excellent electrochemical performance can be efficiently achieved via three-dimensional （3D） architectures decorated with conductive polymers and carbon. As such, we developed 3D carbon-supported amorphous vanadium oxide microspheres and crystalline V203 microspheres via a facile solvothermal method. Both samples were assembled with ultrathin nanosheets, which consisted of uniformly distributed vanadium oxides and carbon. The formation processes were clearly revealed through a series of time-dependent experiments. These microspheres have numerous active reaction sites, high electronic conductivity, and excellent structural stability, which are all far superior to those of other lithium-ion battery anodes. More importantly, 95% of the second-cycle discharge capacity was retained after the amorphous microspheres were subjected to 7,000 cycles at a high rate of 2,000 mA/g. The crystalline microspheres also exhibited a high-rate and long-life performance, as evidenced by a 98% retention of the second-cycle discharge capacity after 9,000 cycles at a rate of 2,000 mA/g. Therefore, this facile solvothermal method as well as unique carbon-supported and nanosheet-assembled microspheres have significant potential for the synthesis of and use in, respectively, lithium-ion batteries.
The cobalt phosphate-/cobalt borate-based oxygen-evolving catalysts （OECs） are the important class of earth-abundant electrocatalysts that can operate with high activity for water splitting under benign conditions. This article reports the integration of cobalt phosphate （Co- Pi） and cobalt borate （Co-Bi） OECs with three-dimensional （3D） graphene foam （GF） for the electrocatalytic water oxidation reaction. The GF showed a unique advantage to serve as a highly conductive 3D support with large capacity for anchoring and loading Co-OECs, thereby facilitating mass and charge transfer due to the large amount of active sites provided by the 3D graphene scaffold. As a result, this integrated system of GF and Co-OECs exhibits synergistically enhanced catalytic activity. The overpotential （η） of Co-Pi and Co-Bi/graphene catalysts is about 0.390 and 0.315 V in neutral solutions, respectively. Besides, the integrated Co-OECs/graphene catalysts have also exhibited improved and stable oxygen evolution catalytic ability in alkaline solution.
Min ZengHao WangChong ZhaoJiake WeiWenlong WangXuedong Bai
Nanowires are promising candidates for energy storage devices such as lithium-ion batteries, su- per（：apa.citors and lithium-air batteries. However, simple-structured nanowires have some limitations hence the strategies to make improvements need to be explored and investigated. Hierarchical nanowires with enhanced periormanee have been considered as an ideal candidate for energy storage due to the novel structures and/or synergistic properties. This review describes some of the recent progresses in the hierarchical nanowire merits, classification, synthesis and performance in energy storage applieat, ions. Herein we discuss the hierarchical nanowires based on their structural design from three major categories, including exterior design, interior design and aligned nanowire assembly. This review also briefly outlines the prospects of hierarchical nanowires in morphology control, property enhancement and application versatility.
Planar micro-supercapacitors （MSCs） have drawn extensive research attention owing to their unique structural design and size compatibility for microelectronic devices. Graphene has been widely used to improve the performance of microscale electrochemical capacitors. However, investigations of an intrinsic electrochemical mechanism for graphene-based microscale devices are still not sufficient. Here, micro-supercapacitors with various typical architectures are fabricated as models to study the graphene effect, and their electrochemical performance is also evaluated. The results show that ionic accessibility and adsorption are greatly improved after the introduction of the holey graphene intermediate layer. This study provides a new route to understand intrinsic electrochemical behaviors and possesses exciting potential for highly efficient on-chip micro-energy storage.
Xiaocong TianBei XiaoXu XuLin XuZehua LiuZhaoyang WangMengyu YanQiulong WeiLiqiang Mai
Metal oxide hollow structures with multilevel interiors are of great interest for potential applications such as catalysis, chemical sensing, drug delivery, and energy storage. However, the controlled synthesis of multilevel nanotubes remains a great challenge. Here we develop a facile interface-modulated approach toward the synthesis of complex metal oxide multilevel nanotubes with tunable interior structures through electrospinning followed by controlled heat treatment. This versatile strategy can be effectively applied to fabricate wire-in-tube and tube- in-tube nanotubes of various metal oxides. These multilevel nanotubes possess a large specific surface area, fast mass transport, good strain accommodation, and high packing density, which are advantageous for lithium-ion batteries （LIBs） and the oxygen reduction reaction （ORR）. Specifically, shrinkable CoMn204 tube-in-tube nanotubes as a lithium-ion battery anode deliver a high discharge capacity of -565 mAh-g-1 at a high rate of 2 A.g-~, maintaining 89% of the latter after 500 cycles. Further, as an oxygen reduction reaction catalyst, these nanotubes also exhibit excellent stability with about 92% current retention after 30,000 s, which is higher than that of commercial Pt/C （81%）. Therefore, this feasible method may push the rapid development of one-dimensional （1D） nanomaterials. These multifunctional nanotubes have great potential in many frontier fields.
