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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.

Nanowire electrodes for electrochemical energy storage devices.

Liqiang Mai,*,† Xiaocong Tian,† Xu Xu,† Liang Chang,‡ and Lin Xu†,§ †State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, WUT-Harvard Joint Nano Key Laboratory, Wuhan University of Technology, Wuhan 430070, China ‡Department of Materials Science and Engineering, Michigan Technological University, Houghton, Michigan 49931-1295, United States Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States

Effect of Carbon Matrix Dimensions on the Electrochemical Properties of Na3V2(PO4)3 Nanograins for High‐Performance Symmetric Sodium‐Ion Batteries

Na3V2(PO4)3 nanograins dispersed in different carbon matrices are rationally synthesized and systematically characterized. The acetylene carbon matrix provides the best conductive networks for electrons and sodium ions, which endows Na3V2(PO4)3 stable cyclability and high rate performance. The Na3V2 (PO4)3 -based symmetric sodium-ion batteries show outstanding electrochemical performance, which is promising for large-scale and low-cost energy storage applications.

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.

Three-dimensional holey-graphene/niobia composite architectures for ultrahigh-rate energy storage

As with donuts, the holes matter Improving the density of stored charge and increasing the speed at which it can move through a material are usually opposing objectives. Sun et al. developed a Nb2O5/holey graphene framework composite with tailored porosity. The three-dimensional, hierarchically porous holey graphene acted as a conductive scaffold to support Nb2O5. A high mass loading and improved power capability were reached by tailoring the porosity in the holey graphene backbone with higher charge transport in the composite architecture. The interconnected graphene network provided excellent electron transport, and the hierarchical porous structure in the graphene sheets facilitated rapid ion transport and mitigated diffusion limitations. Science, this issue p. 599 A graphene/Nb2O5 composite shows optimized electron and ion transport. Nanostructured materials have shown extraordinary promise for electrochemical energy storage but are usually limited to electrodes with rather low mass loading (~1 milligram per square centimeter) because of the increasing ion diffusion limitations in thicker electrodes. We report the design of a three-dimensional (3D) holey-graphene/niobia (Nb2O5) composite for ultrahigh-rate energy storage at practical levels of mass loading (>10 milligrams per square centimeter). The highly interconnected graphene network in the 3D architecture provides excellent electron transport properties, and its hierarchical porous structure facilitates rapid ion transport. By systematically tailoring the porosity in the holey graphene backbone, charge transport in the composite architecture is optimized to deliver high areal capacity and high-rate capability at high mass loading, which represents a critical step forward toward practical applications.

Solution Processable Holey Graphene Oxide and Its Derived Macrostructures for High-Performance Supercapacitors

Scalable preparation of solution processable graphene and its bulk materials with high specific surface areas and designed porosities is essential for many practical applications. Herein, we report a scalable approach to produce aqueous dispersions of holey graphene oxide with abundant in-plane nanopores via a convenient mild defect-etching reaction and demonstrate that the holey graphene oxide can function as a versatile building block for the assembly of macrostructures including holey graphene hydrogels with a three-dimensional hierarchical porosity and holey graphene papers with a compact but porous layered structure. These holey graphene macrostructures exhibit significantly improved specific surface area and ion diffusion rate compared to the nonholey counterparts and can be directly used as binder-free supercapacitor electrodes with ultrahigh specific capacitances of 283 F/g and 234 F/cm(3), excellent rate capabilities, and superior cycling stabilities. Our study defines a scalable pathway to solution processable holey graphene materials and will greatly impact the applications of graphene in diverse technological areas.

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.

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.