Yunlong Zhao

Electrospun Ultralong Hierarchical Vanadium Oxide Nanowires with High Performance for Lithium Ion Batteries

Ultralong hierarchical vanadium oxide nanowires with diameter of 100-200 nm and length up to several millimeters were synthesized using the low-cost starting materials by electrospinning combined with annealing. The hierarchical nanowires were constructed from attached vanadium oxide nanorods of diameter around 50 nm and length of 100 nm. The initial and 50th discharge capacities of the ultralong hierarchical vanadium oxide nanowire cathodes are up to 390 and 201 mAh/g when the lithium ion battery cycled between 1.75 and 4.0 V. When the battery was cycled between 2.0 and 4.0 V, the initial and 50th discharge capacities of the nanowire cathodes are 275 and 187 mAh/g. Compared with self-aggregated short nanorods synthesized by hydrothermal method, the ultralong hierarchical vanadium oxide nanowires exhibit much higher capacity. This is due to the fact that self-aggregation of the unique nanorod-in-nanowire structures have been greatly reduced because of the attachment of nanorods in the ultralong nanowires, which can keep the effective contact areas of active materials, conductive additives, and electrolyte large and fully realize the advantage of nanomaterial-based cathodes. This demonstrates that ultralong hierarchical vanadium oxide nanowire is one of the most favorable nanostructures as cathodes for improving cycling performance of lithium ion batteries.

Synergistic interaction between redox-active electrolyte and binder-free functionalized carbon for ultrahigh supercapacitor performance

Development of supercapacitors with high-energy density and high-power density is a tremendous challenge. Although the use of conductive carbon materials is promising, other methods are needed to reach high cyclability, which cannot be achieved by fully utilizing the surface-oxygen redox reactions of carbon. Here we introduce an effective strategy that utilizes Cu(2+) reduction with carbon-oxygen surface groups of the binder-free electrode in a new redox-active electrolyte. We report a 10-fold increase in the voltammetric capacitance (4,700 F g(-1)) compared with conventional electrolyte. We measured galvanostatic capacitances of 1,335 F g(-1) with a retention of 99.4% after 5,000 cycles at 60 A g(-1) in a three-electrode cell and 1,010 F g(-1) in a two-electrode cell. This improvement is attributed to the synergistic effects between surface-oxygen molecules and electrolyte ions as well as the low charge transfer resistance (0.04 Ω) of the binder-free porous electrode. Our strategy provides a versatile method for designing new energy storage devices and is promising for the development of high-performance supercapacitors for large-scale applications.

Hierarchical mesoporous perovskite La0.5Sr0.5CoO2.91 nanowires with ultrahigh capacity for Li-air batteries

Lithium-air batteries have captured worldwide attention due to their highest energy density among the chemical batteries. To provide continuous oxygen channels, here, we synthesized hierarchical mesoporous perovskite La0.5Sr0.5CoO2.91 (LSCO) nanowires. We tested the intrinsic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity in both aqueous electrolytes and nonaqueous electrolytes via rotating disk electrode (RDE) measurements and demonstrated that the hierarchical mesoporous LSCO nanowires are high-performance catalysts for the ORR with low peak-up potential and high limiting diffusion current. Furthermore, we fabricated Li-air batteries on the basis of hierarchical mesoporous LSCO nanowires and nonaqueous electrolytes, which exhibited ultrahigh capacity, ca. over 11,000 mAh⋅g –1, one order of magnitude higher than that of LSCO nanoparticles. Besides, the possible reaction mechanism is proposed to explain the catalytic activity of the LSCO mesoporous nanowire.

One-Pot Synthesized Bicontinuous Hierarchical Li3V2(PO4)3/C Mesoporous Nanowires for High-Rate and Ultralong-Life Lithium-ion Batteries

Lithium-ion batteries have attracted enormous attention for large-scale and sustainable energy storage applications. Here we present a design of hierarchical Li3V2(PO4)3/C mesoporous nanowires via one-pot synthesis process. The mesoporous structure is directly in situ carbonized from the surfactants (CTAB and oxalic acid) along with the crystallization of Li3V2(PO4)3 without using any hard templates. As a cathode for lithium-ion battery, the Li3V2(PO4)3/C mesoporous nanowires exhibit outstanding high-rate and ultralong-life performance with capacity retention of 80.0% after 3000 cycles at 5 C in 3-4.3 V. Even at 10 C, it still delivers 88.0% of its theoretical capacity. The ability to provide this level of performance is attributed to the hierarchical mesoporous nanowires with bicontinuous electron/ion pathways, large electrode-electrolyte contact area, low charge transfer resistance, and robust structure stability upon prolonged cycling. Our work demonstrates that the unique mesoporous nanowires structure is favorable for improving the cyclability and rate capability in energy storage applications.

General synthesis of complex nanotubes by gradient electrospinning and controlled pyrolysis

Nanowires and nanotubes have been the focus of considerable efforts in energy storage and solar energy conversion because of their unique properties. However, owing to the limitations of synthetic methods, most inorganic nanotubes, especially for multi-element oxides and binary-metal oxides, have been rarely fabricated. Here we design a gradient electrospinning and controlled pyrolysis method to synthesize various controllable 1D nanostructures, including mesoporous nanotubes, pea-like nanotubes and continuous nanowires. The key point of this method is the gradient distribution of low-/middle-/high-molecular-weight poly(vinyl alcohol) during the electrospinning process. This simple technique is extended to various inorganic multi-element oxides, binary-metal oxides and single-metal oxides. Among them, Li3V2(PO4)3, Na0.7Fe0.7Mn0.3O2 and Co3O4 mesoporous nanotubes exhibit ultrastable electrochemical performance when used in lithium-ion batteries, sodium-ion batteries and supercapacitors, respectively. We believe that a wide range of new materials available from our composition gradient electrospinning and pyrolysis methodology may lead to further developments in research on 1D systems.

Nanoscroll Buffered Hybrid Nanostructural VO2 (B) Cathodes for High‐Rate and Long‐Life Lithium Storage

Hybrid nanostructural VO2 (B) composed of nanoscrolls, nanobelts and nanowires is synthesized through a hydrothermal-driven splitting and self-rolled method. The hybrid nanostructure with nanoscroll buffered effect provides facile strain relaxation for swelling during lithiation/delithiation, resulting in the excellent structural stability and cyclability. The interior of nanoscrolls and the interconnected voids shorten the ion diffusion pathway, which greatly enhances the rate performance.

Cucumber-Like V2O5/poly(3,4-ethylenedioxythiophene)&MnO2 Nanowires with Enhanced Electrochemical Cyclability

Inspired by the cucumber-like structure, by combining the in situ chemical oxidative polymerization with facile soaking process, we designed the heterostructured nanomaterial with PEDOT as the shell and MnO(2) nanoparticles as the protuberance and synthesized the novel cucumber-like MnO(2) nanoparticles enriched vanadium pentoxide/poly(3,4-ethylenedioxythiophene) (PEDOT) coaxial nanowires. This heterostructured nanomaterial exhibits enhanced electrochemical cycling performance with the decreases of capacity fading during 200 cycles from 0.557 to 0.173% over V(2)O(5) nanowires at the current density of 100 mA/g. This method is proven to be an effective technique for improving the electrochemical cycling performance and stability of nanowire electrodes especially at low rate for application in rechargeable lithium batteries.

Synergistic Effect of Hierarchical Nanostructured MoO2/Co(OH)2 with Largely Enhanced Pseudocapacitor Cyclability

Pseudocapacitors have demonstrated an ability to deliver high energy and power densities. The main limitation is their poor cyclability and for this reason the architectural design of electrode materials has attracted considerable attention. Here we report the synthesis of hierarchical nanostructured material by growing Co(OH)2 nanoflakes onto MoO2 thin film. The electrode material exhibits a high capacitance of 800 F g(-1) at 20 A g(-1) with only 3% capacitance loss after 5000 cycles and high rate capability with increasing current density from 2 to 40 A g(-1), which are better than those of individual component. The enhanced pseudocapacitor performances benefit from the synergistic effect of the hierarchical nanostructure: (1) faster ion diffusion and electron transport at electrode/electrolyte interface, and (2) mitigation of the electrode destruction caused by ion insertion/deinsertion during charge-storage process. This facile design and rational synthesis offers an effective strategy to enhance the electrochemical performance of pseudocapacitors and shows promising potential for large-scale application in energy storage.

Fast Ionic Diffusion-Enabled Nanoflake Electrode by Spontaneous Electrochemical Pre-Intercalation for High-Performance Supercapacitor

Layered intercalation compounds NaxMnO2 (x = 0.7 and 0.91) nanoflakes have been prepared directly through wet electrochemical process with Na+ ions intercalated into MnO2 interlayers spontaneously. The as-prepared NaxMnO2 nanoflake based supercapacitors exhibit faster ionic diffusion with enhanced redox peaks, tenfold-higher energy densities up to 110 Wh·kg−1 and higher capacitances over 1000 F·g−1 in aqueous sodium system compared with traditional MnO2 supercapacitors. Due to the free-standing electrode structure and suitable crystal structure, NaxMnO2 nanoflake electrodes also maintain outstanding electrochemical stability with capacitance retention up to 99.9% after 1000 cycles. Besides, pre-intercalation effect is further studied to explain this enhanced electrochemical performance. This study indicates that the suitable pre-intercalation is effective to improve the diffusion of electrolyte cations and other electrochemical performance for layered oxides, and suggests that the as-obtained nanoflakes are promising materials to achieve the hybridization of both high energy and power density for advanced supercapacitors.

Interwoven Three-Dimensional Architecture of Cobalt Oxide Nanobrush-Graphene@NixCo2x(OH)6x for High-Performance Supercapacitors

Development of pseudocapacitor electrode materials with high comprehensive electrochemical performance, such as high capacitance, superior reversibility, excellent stability, and good rate capability at the high mass loading level, still is a tremendous challenge. To our knowledge, few works could successfully achieve the above comprehensive electrochemical performance simultaneously. Here we design and synthesize one interwoven three-dimensional (3D) architecture of cobalt oxide nanobrush-graphene@Ni(x)Co(2x)(OH)(6x) (CNG@NCH) electrode with high comprehensive electrochemical performance: high specific capacitance (2550 F g(-1) and 5.1 F cm(-2)), good rate capability (82.98% capacitance retention at 20 A g(-1) vs 1 A g(-1)), superior reversibility, and cycling stability (92.70% capacitance retention after 5000 cycles at 20 A g(-1)), which successfully overcomes the tremendous challenge for pseudocapacitor electrode materials. The asymmetric supercapacitor of CNG@NCH//reduced-graphene-oxide-film exhibits good rate capability (74.85% capacitance retention at 10 A g(-1) vs 0.5 A g(-1)) and high energy density (78.75 Wh kg(-1) at a power density of 473 W kg(-1)). The design of this interwoven 3D frame architecture can offer a new and appropriate idea for obtaining high comprehensive performance electrode materials in the energy storage field.