Chaolun Liang

High energy density asymmetric quasi-solid-state supercapacitor based on porous vanadium nitride nanowire anode.

To push the energy density limit of asymmetric supercapacitors (ASCs), a new class of anode materials is needed. Vanadium nitride (VN) holds great promise as anode material for ASCs due to its large specific capacitance, high electrical conductivity, and wide operation windows in negative potential. However, its poor electrochemical stability severely limits its application in SCs. In this work, we demonstrated high energy density, stable, quasi-solid-state ASC device based on porous VN nanowire anode and VOx nanowire cathode for the first time. The VOx//VN-ASC device exhibited a stable electrochemical window of 1.8 V and excellent cycling stability with only 12.5% decrease of capacitance after 10,000 cycles. More importantly, the VOx//VN-ASC device achieved a high energy density of 0.61 mWh cm(-3) at current density of 0.5 mA cm(-2) and a high power density of 0.85 W cm(-3) at current density of 5 mA cm(-2). These values are substantially enhanced compared to most of the reported quasi/all-solid-state SC devices. This work constitutes the first demonstration of using VN nanowires as high energy anode, which could potentially improve the performance of energy storage devices.

Stabilized TiN Nanowire Arrays for High-Performance and Flexible Supercapacitors

Metal nitrides have received increasing attention as electrode materials for high-performance supercapacitors (SCs). However, most of them are suffered from poor cycling stability. Here we use TiN as an example to elucidate the mechanism causing the capacitance loss. X-ray photoelectron spectroscopy analyses revealed that the instability is due to the irreversible electrochemical oxidation of TiN during the charging/discharging process. Significantly, we demonstrate for the first time that TiN can be stabilized without sacrificing its electrochemical performance by using poly(vinyl alcohol) (PVA)/KOH gel as the electrolyte. The polymer electrolyte suppresses the oxidation reaction on electrode surface. Electrochemical studies showed that the TiN solid-state SCs exhibit extraordinary stability up to 15,000 cycles and achieved a high volumetric energy density of 0.05 mWh/cm(3). The capability of effectively stabilizing nitride materials could open up new opportunities in developing high-performance and flexible SCs.

Oxygen‐Deficient Hematite Nanorods as High‐Performance and Novel Negative Electrodes for Flexible Asymmetric Supercapacitors

Oxygen-deficient α-Fe2 O3 nanorods with outstanding capacitive performance are developed and demonstrated as novel negative electrodes for flexible asymmetric supercapacitors. The asymmetric-supercapacitor device based on the oxygen-deficient α-Fe2 O3 nanorod negative electrode and a MnO2 positive electrode achieves a maximum energy density of 0.41 mW·h/cm(3) ; it is also capable of charging a mobile phone and powering a light-emitting diode indicator.

A New Benchmark Capacitance for Supercapacitor Anodes by Mixed‐Valence Sulfur‐Doped V6O13−x

A new pseudocapacitor anode, sulfur-doped V6O(13-x), is reported. It achieves a benchmark capacitance of 1353 F/g (0.72 F/cm(2)) at a current density of 1.9 A/g (1 mA/cm(2)) in 5 M LiCl solution. The charges are stored chemically in the electrode via reversible redox reactions that involve multiple oxidation states of vanadium (V(3+), V(4+) and V(5+)).

Formation Mechanism of CaTiO3 Hollow Crystals with Different Microstructures

The crystal growth of CaTiO(3) hollow crystals with different microstructures has been investigated. In a water-free poly(ethylene glycol) 200 (PEG-200) solution, CaTiO(3) nanocubes formed first. The nanocubes underwent an oriented self-assembly into spherical particles, enhanced by the surface-adsorbed polymer molecules. Since the growth of nanocubes and their aggregation took place simultaneously, the nanocubes in the outer shells were larger than those in the cores. Disappearance of the small nanocubes in the cores of the spheres during an Ostwald ripening process led to spherical hollow crystals. Addition of a small amount of water (1.25 vol %) in the polymer solution enhanced surface recrystallization of the aggregated spheres, forming a cubic morphology. The orthorhombic distortion of the perovskite CaTiO(3) structure did not have a significant effect on the nanocube aggregation, resulting in a domain structure in the shells. Single-crystalline hollow cubes were produced with a slightly higher water content, e.g., 5 vol %. This process of (1) aggregation of nanocubes and (2) surface crystallization followed by (3) surface-to-core extension of recrystallization gives a good example of the reversed crystal growth route in ceramic materials. The proposed formation mechanism of the hollow CaTiO(3) crystals would enable us to control the microstructures of these materials and to explain the formation of many other hollow crystals.

Controllable synthesis of porous nickel-cobalt oxide nanosheets for supercapacitors†

Vertically aligned nickel–cobalt oxide (NCO) nanosheets with porous structure were successfully synthesized on FTO substrates by a simple electrochemical method without any templates. Cyclic voltammetry (CV) and galvanostatic charge/discharge measurements show that the porous NCO nanosheets have an ideal capacitive performance and long-term stability. With an optimum amount of Ni, the specific capacitance for the NCOs could reach as high as 453 F g−1 at a scan rate of 5 mV s−1 and 506 F g−1 at a current density of 1 A g−1, showing an improvement of around 50% compared with cobalt oxide. Furthermore, a symmetric supercapacitor based on two NCO electrodes exhibits a maximum specific capacitance of 89.2 F g−1 at 0.17 A g−1.

TiO2@C core–shell nanowires for high-performance and flexible solid-state supercapacitors

A flexible and solid-state supercapacitor device based on TiO2@C core–shell nanowires has been developed and exhibited excellent flexibility—it can even be folded and twisted without sacrificing electrochemical properties—and good electrochemical performance with a maximum energy density of 0.011 mW h cm−3.

Continuous shape- and spectroscopy-tuning of hematite nanocrystals.

Uniform hexagonal hematite (α-Fe(2)O(3)) nanoplates have been synthesized by a facile alcohol-thermal reaction, and a new nanostructure of α-Fe(2)O(3) has been proposed. Each nanoplate is enclosed by (0001) basal planes and {1012} side surfaces. The phase, size, shape, and growth orientation of these nanocrystals were characterized by powder X-ray diffraction and electron microscopy. The thickness and diameter of these nanocrystals could be finely tuned by the selective use of alcohol solvent with increasing carbon atom number in the linear alkyl chain. A variety of nanocrystals with systemically changeable shapes from nanoplates to nanograins have been obtained. Specific adsorption of alcohol molecules on polar (0001) facets is proposed to be the main issue to modify the growth behavior of hematite nanocrystals. The presence of distilled water and the addition of sodium acetate have also been investigated. Either of them has a great influence on the growth of hematite nanocrystals, and shape-controlled growth can be rationally achieved. In addition, the post-aging of as-grown hematite nanocrystals in alcohol and distilled water has also been described. Both vibration spectroscopy (i.e., FTIR and Raman) and electronic spectra (diffused reflectance spectra) of these nanocrystals with a continuing shape change show a highly shape-dependent nature.

Nitrogen-Doped Co3O4 Mesoporous Nanowire Arrays as an Additive-Free Air-Cathode for Flexible Solid-State Zinc–Air Batteries

The kinetically sluggish rate of oxygen reduction reaction (ORR) on the cathode side is one of the main bottlenecks of zinc-air batteries (ZABs), and thus the search for an efficient and cost-effective catalyst for ORR is highly pursued. Co3 O4 has received ever-growing interest as a promising ORR catalyst due to the unique advantages of low-cost, earth abundance and decent catalytic activity. However, owing to the poor conductivity as a result of its semiconducting nature, the ORR activity of the Co3 O4 catalyst is still far below the expectation. Herein, we report a controllable N-doping strategy to significantly improve the catalytic activity of Co3 O4 for ORR and demonstrate these N doped Co3 O4 nanowires as an additive-free air-cathode for flexible solid-state zinc-air batteries. The results of experiments and DFT calculations reveal that the catalytic activity is promoted by the N dopant through a combined set of factors, including enhanced electronic conductivity, increased O2 adsorption strength and improved reaction kinetics. Finally, the assembly of all-solid-state ZABs based on the optimized cathode exhibit a high volumetric capacity of 98.1 mAh cm-3 and outstanding flexibility. The demonstration of such flexible ZABs provides valuable insights that point the way to the redesign of emerging portable electronics.

Hierarchically Nanostructured Rutile Arrays: Acid Vapor Oxidation Growth and Tunable Morphologies

A general acid vapor oxidation (AVO) strategy has been developed to grow highly oriented hierarchically structured rutile TiO(2) nanoarrays with tunable morphologies from titanium thin films. This is a simple one-pot synthesis approach involving the reaction of a titanium surface with the vapor generated from a hydrochloric acid solution in a Teflon lined autoclave. To the best of our knowledge, this is the first successful attempt to grow ordered tree-like titania nanoarrays. A possible formation mechanism for the interesting architectures has been proposed based on series of time-dependent experiments. By adjusting the initial HCl concentration, films of different rutile structures including nanotrees, dendritic nanobundles, and nanorods can be selectively obtained. Subsequently, the surface morphologies and wettability can be readily tuned.