Methylboronic acid MIDA ester (ADM) as an effective additive in electrolyte to improve cathode electrolyte interlayer performance of LiNi0.8Co0.15Al0.05O2 electrode.

We investigated the effectiveness of using methylboronic acid MIDA ester (ADM) as an additive in an electrolyte to enhance the overall electrochemical and material properties of an LNCAO (LiNi0.8Co0.15Al0.05O2) cathode. The cyclic stability of the cathode material measured at 40 °C (@ 0.2 C) showed an enhanced capacity of 144.28 mAh g-1 (@ 100 cycles), a capacity retention of 80%, and a high coulombic efficiency (99.5%), in contrast to these same properties without the electrolyte additive (37.5 mAh g-1, ~ 20%, and 90.4%), thus confirming the effectiveness of the additive. A Fourier transform infrared spectroscopy (FTIR) analysis distinctly showed that the ADM additive suppressed the EC-Li+ ion coordination (1197 cm-1 and 728 cm-1) in the electrolyte, thereby improving the cyclic performance of the LNCAO cathode. The cathode after 100 charge/discharge cycles revealed that the ADM-containing system exhibited better surface stability of the grains in the LNCAO cathode, whereas distinct cracks were observed in the system without the ADM in the electrolyte. A transmission electron microscopy (TEM) analysis revealed the presence of a thin, uniform and dense cathode electrolyte interface (CEI) film on the surface of LNCAO cathode. An operando synchrotron X-ray diffraction (XRD) test identified the high structural reversibility of the LNCAO cathode with a CEI layer formed by the ADM, which effectively maintained the structural stability of the layered material. The additive effectively inhibited the decomposition of electrolyte compositions, as confirmed by X-ray photoelectron spectroscopy (XPS).

Synergistic effects of Ga doping and Mg alloying over the enhancement of the stress sensitivity of a Ga-doped MgZnO pressure sensor.

We demonstrate the synergistic effects of Ga doping and Mg alloying into ZnO on the large enhancement of the piezopotential and stress sensing performance of piezotronic pressure sensors made of Ga-doped MgZnO films. Piezopotential-induced pressure sensitivity was enhanced through the modulation of the Schottky barrier height. Doping with Ga (0.62 Å) of larger ionic radius and alloying with Mg (0.57 Å) of smaller ionic radius than Zn ions can synergistically affect the overall structural, optical and piezoelectric properties of the resulting thin films. The crystal quality of Ga-doped MgZnO films either improved (X Ga ≦ 0.041) or deteriorated (X Ga ≧ 0.041) depending on the Ga doping concentration. The band gap increased from 3.90 eV for pristine MgZnO to 3.93 eV at X Ga = 0.076, and the piezoelectric coefficient (d 33) improved from ∼23.25 pm V-1 to ∼33.17 pm V-1 at an optimum Ga concentration (X Ga = 0.027) by ∼2.65 times. The change in the Schottky barrier height ΔΦ b increased from -4.41 meV (MgZnO) to -4.81 meV (X Ga = 0.027) and decreased to -3.99 meV at a high Ga doping concentration (X Ga = 0.041). The stress sensitivity (0.2 kgf) enhanced from 28.50 MPa-1 for the pristine MgZnO to 31.36 MPa-1 (X Ga = 0.027) and decreased to 25.56 MPa-1 at higher Ga doping concentrations, indicating the synergistic effects of Ga doping and Mg alloying over the pressure sensing performance of Ga-doped MgZnO films.

MoS2-Carbon Inter-overlapped Structures as Effective Electrocatalysts for the Hydrogen Evolution Reaction.

The ability to generate hydrogen in an economic and sustainable manner is critical to the realization of a future hydrogen economy. Electrocatalytic water splitting into molecular hydrogen using the hydrogen evolution reaction (HER) provides a viable option for hydrogen generation. Consequently, advanced non-precious metal based electrocatalysts that promote HER and reduce the overpotential are being widely researched. Here, we report on the development of MoS2-carbon inter-overlapped structures and their applicability for enhancing electrocatalytic HER. These structures were synthesized by a facile hot-injection method using ammonium tetrathiomolybdate ((NH4)2MoS4) as the precursor and oleylamine (OLA) as the solvent, followed by a carbonization step. During the synthesis protocol, OLA not only plays the role of a reacting solvent but also acts as an intercalating agent which enlarges the interlayer spacing of MoS2 to form OLA-protected monolayer MoS2. After the carbonization step, the crystallinity improves substantially, and OLA can be completely converted into carbon, thus forming an inter-overlapped superstructure, as characterized in detail using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). A Tafel slope of 118 mV/dec is obtained for the monolayer MoS2-carbon superstructure, which shows a significant improvement, as compared to the 202 mV/dec observed for OLA-protected monolayer MoS2. The enhanced HER performance is attributed to the improved conductivity along the c-axis due to the presence of carbon and the abundance of active sites due to the interlayer expansion of the monolayer MoS2 by OLA.

Cyclability evaluation on Si based Negative Electrode in Lithium ion Battery by Graphite Phase Evolution: an operando X-ray diffraction study.

Artificial graphite (FSN) additive is employed as internal structural label for projecting cyclability of Si material native electrode in a mass ratio of Si/FSN = 1.0 in Li ion battery (LIB). Results of operando X-ray diffraction analysis on Si-FSN negative electrode in LIB demonstrate that one can evaluate the lithiation and delithiation affinity of active material by referring phase transition delay of graphite as affected by experimental splits in a formation process of LIB. We prove that a thin layer of surface amorphous structure and residual lattice strain are formed in Si by high energy ball-milling treatment. Those manipulations improve Li intercalation kinetics and thus enabling a capacity fading of less than 10% (from 1860 to 1650 mAhg-1) for Si negative electrode in 50 cycles. Of utmost importance, this study discloses a robust assessment for revealing mechanism on amorphous and strain related silicide formation and predicting cyclability of negative electrode by quantitative phase evolution rate of FSN additive in LIB.

Mechanochemical synthesis of Si/Cu3Si-based composite as negative electrode materials for lithium ion battery.

Mechanochemical synthesis of Si/Cu3Si-based composite as negative electrode materials for lithium ion battery is investigated. Results indicate that CuO is decomposed and alloyed with Si forming amorphous Cu-Si solid solution due to high energy impacting during high energy mechanical milling (HEMM). Upon carbonization at 800 °C, heating energy induces Cu3Si to crystallize in nanocrystalline/amorphous Si-rich matrix enhancing composite rigidity and conductivity. In addition, residual carbon formed on outside surface of composite powder as a buff space further alleviates volume change upon lithiation/delithiation. Thus, coin cell made of C-coated Si/Cu3Si-based composite as negative electrode (active materials loading, 2.3 mg cm-2) conducted at 100 mA g-1 performs the initial charge capacity of 1812 mAh g-1 (4.08 mAh cm-2) columbic efficiency of 83.7% and retained charge capacity of 1470 mAh g-1 (3.31 mAh cm-2) at the end of the 100th cycle, opening a promised window as negative electrode materials for lithium ion batteries.

Effect of Annealing Temperature and Oxygen Flow in the Properties of Ion Beam Sputtered SnO-2x Thin Films.

Tin oxide (SnO2-x) thin films were prepared under various flow ratios of O2/(O2 + Ar) on unheated glass substrate using the ion beam sputtering (IBS) deposition technique. This work studied the effects of the flow ratio of O2/(O2 + Ar), chamber pressures and post-annealing treatment on the physical properties of SnO2 thin films. It was found that annealing affects the crystal quality of the films as seen from both X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis. In addition, the surface RMS roughness was measured with atomic force microscopy (AFM). Auger electron spectroscopy (AES) analysis was used to obtain the changes of elemental distribution between tin and oxygen atomic concentration. The electrical property is discussed with attention to the structure factor.

Spinodal decomposition of mono- to few-layer graphene on Ni substrates at low temperature.

Mono to few-layer graphene were prepared on pre-annealed polycrystalline nickel substrates by chemical vapor deposition at a relatively low temperature of 800 degrees C using fast cooling rate. It was observed that the reduced solubility of Carbon in Ni at low temperature and an optimum gas mixing ratio (CH4:H2 = 60/80 (sccm)) can be used to synthesize mano-layer graphene that covers about 100 microm2 area. The number of graphene layers strongly depends upon the hydrogen and methane flow rates. An increase in the methane flow is found to increase the growth density of the single-layer graphene. The number of graphene layers was identified from micro-Raman spectra. The thinnest areas containing mono-layer graphene formed at small Ni grains surrounded by large Ni Grains can be explained in terms of Spinodal decomposition. Scanning tunneling microscopy observations of the graphene samples indicate that the graphene structure exhibits no defects, and extremely symmetry hexagon carbon at flat graphene surface is observed.

Observation of quantum confinement effect on ZnO embedded mesoporous silica.

Nonionic surfactant as liquid organic template and tetraethoxysilane as silica precursor were used for the synthesis of mesoporous silica with ordered arrangement of nanopores (diameters are about 1-6 nm). The synthesized mesoporous silica was used as the template for the synthesis of ZnO nanoparticles using zinc acetylacetonate as ZnO precursor. The as synthesized ZnO incorporated in the mesoporous silica nanocomposite were analyzed using X-ray diffraction, TEM and Photoluminescent spectrum. ZnO introduction has no extensive influence on the mesoporous structure of silica. Quantum confinement effects are observed in the case of ZnO nanoparticles embedded in mesoporous silica. The particle size of ZnO is about 3.2 nm. The band gap is broadening to 3.47 eV.

Enhanced density control of Al:ZnO nanowires via one-by-one coupling of nanowires and pyramids.

Al doped ZnO nanowire arrays with controlled growth densities were fabricated on silicon without using catalysts via sputtering followed by thermal chemical vapor deposition (CVD). Scanning electron microscopy and high-resolution transmission electron microscopy results show that the Al:ZnO single-crystalline nanowires synthesized by CVD prefer growing epitaxially on the tips of the ZnO pyramids pre-synthesized by sputtering with the c-axis perpendicular to the substrate. Consequently, the densities of the as-grown Al:ZnO nanowires were controllable by changing the particle densities of the pre-grown ZnO seed layers. The Al concentration of the Al:ZnO nanowires were measured to be around 2.63 at.% by electron energy loss spectrum. Field-emission measurements show the turn-on fields of the Al:ZnO nanowire arrays with controllable area densities are tunable. Room-temperature cathodoluminescence spectra of the Al:ZnO nanowires show relatively strong and sharp ultraviolet emissions centered at 383 nm and broad green emissions at around 497 nm. This work provides a simple method to control the field emission and luminescence densities of Al doped ZnO nanowire arrays, which also shows good potential for developing nano-pixel optical devices.

The synthesis and electrical characterization of Cu2O/Al:ZnO radial p-n junction nanowire arrays.

Vertically aligned large-area p-Cu(2)O/n-AZO (Al-doped ZnO) radial heterojunction nanowire arrays were synthesized on silicon without using catalysts in thermal chemical vapor deposition followed by e-beam evaporation. Scanning electron microscopy and high-resolution transmission electron microscopy results show that poly-crystalline Cu(2)O nano-shells with thicknesses around 10 nm conformably formed on the entire periphery of pre-grown Al:ZnO single-crystalline nanowires. The Al doping concentration in the Al:ZnO nanowires with diameters around 50 nm were determined to be around 1.19 at.% by electron energy loss spectroscopy. Room-temperature photoluminescence spectra show that the broad green bands of pristine ZnO nanowires were eliminated by capping with Cu(2)O nano-shells. The current-voltage (I-V) measurements show that the p-Cu(2)O/n-AZO nanodiodes have well-defined current rectifying behavior. This paper provides a simple method to fabricate superior p-n radial nanowire arrays for developing nano-pixel optoelectronic devices and solar cells.

Composition fluctuation induced growth of Al:ZnO rectangular nanorod arrays.

Arrays of single-crystalline Al doped ZnO rectangular nanorods were synthesized and nucleated from single-crystalline ZnO nanosheets by thermal chemical vapor deposition. The rectangular nanorods were grown from the periodic thicker regions of the nanosheets, associated with Al concentration fluctuation and evidenced from electron energy loss spectroscopy. High-resolution transmission electron microscopy also shows variations in the lattice constant and dislocations at the interface due to lattice strain. The composition modulation induced by doping may serve as a driving force for creating interesting nanostructures with tunable properties.

ZnO nanorods with two spatially distinct light emissions.

Single-crystalline ZnO nanorods emitting two characteristic optical emissions from opposite halves of the nanorods were synthesized by thermal chemical vapor deposition using Zn/Al mixed powders. Energy dispersive x-ray spectra with transmission electron microscopy show a gradually decreasing Zn:O atomic ratio from the root to the top of a nanorod, and the averaged ratios at the two ends are ≈57.2:42.8 and 49.5:50.5. Room-temperature cathodoluminescence measurements show that the nanorods exhibit a sharp ultraviolet emission at 377 nm from one segment and a broad green band at 500 nm from the other, which is attributed to different oxygen concentrations along the nanorods. The luminescence behavior suggests further applications for nano-pixel optoelectric devices.