High-performance Sn–Ni alloy nanorod electrodes prepared by electrodeposition for lithium ion rechargeable batteries

To reduce irreversible capacity and improve cycle performance of tin used in lithium ion batteries, Sn–Ni alloy nanorod electrodes with different Sn/Ni ratios were prepared by an anodic aluminum oxide template-assisted electrodeposition method. The structural and electrochemical performance of the electrode were characterized using scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, cyclic voltammetry, and galvanostatic charge–discharge cycling measurement. The results showed that the copper substrate is covered with uniformly distributed Sn–Ni alloy nanorods with an average diameter of 250 nm. Different phases (Sn, Ni₃Sn₄ and metastable phases) of alloy nanorod formed in the electrodeposition baths with different compositions of Sn²⁺ and Ni²⁺ ions. Sn–Ni alloy nanorod electrode delivered excellent capacity retention and rate performance.     

SiC Nanorods Grown on Electrospun Nanofibers Using Tb as Catalyst: Fabrication, Characterization, and Photoluminescence Properties

Well-crystallized β-SiC nanorods grown on electrospun nanofibers were synthesized by carbothermal reduction of Tb doped SiO₂ (SiO₂:Tb) nanofibers at 1,250 °C. The as-synthesized SiC nanorods were 100–300 nm in diameter and 2–3 μm in length. Scanning electron microscopy (SEM) results suggested that the growth of the SiC nanorods should be governed by vapor-liquid-solid (VLS) mechanism with Tb metal as catalyst. Tb(NO₃)₃ particles on the surface of the electrospun nanofibers were decomposed at 500 °C and later reduced to the formation of Tb nanoclusters at 1,200 °C, and finally the formation of a Si–C–Tb ally droplet will stimulate the VLS growth at 1,250 °C. Microstructure of the nanorod was further investigated by transmission electron microscopy (TEM). It was found that SiC <111> is the preferred initial growth direction. The liquid droplet was identified to be Si₈₆Tb₁₄, which acted as effective catalyst. Strong green emissions were observed from the SiC nanorod samples. Four characteristic photoluminescence (PL) peaks of Tb ions were also identified.     

Possible proton conduction in Ce<Subscript>0.9</Subscript>Gd<Subscript>0.1</Subscript>O<Subscript>2−δ</Subscript> nanoceramics

Dense samples of Ce_0.9Gd_0.1O_2−δ with grain sizes in the range 91–252 nm were prepared and their electrical properties studied by impedance spectroscopy. It was found that the bulk conductivity is not affected by grain size or atmosphere and that small grain sizes lead to a larger total resistance of the material. The most striking result corresponds to a sample sintered in wet air that exhibited electrical characteristics that hint clearly at the presence of proton conduction at temperatures below 200 °C.     

An Innovative Synthesis of Calcium Zeolite Type A Catalysts from Eggshells via the Sol–Gel Process

Calcium zeolite type A (CaNaAlSi₂O₇), called soda melilite, with a molar ratio of CaO:Al₂O₃:Na₂O:SiO₂ of 1:1:2:8 and calcined at 300 °C for 1 h was successfully synthesized by a sol–gel process using eggshell as the starting material. The CaNaAlSi₂O₇ catalysts had N₂ adsorption–desorption isotherms and good electrical properties. The specific surface area, pore volume, and average pore diameter were 55.15 m²/g, 0.51, and 37.19 nm, respectively. The dielectric constant, electrical conductivity, and loss tangent are 46.5785, 5.2360 × 10⁻³ (Ω m)⁻¹, and 2.75, respectively as measured at room temperature and at 1000 kHz (1 MHz). The transmission electron microscopy (TEM) images showed a moderately good dispersion of uniform particles with an average diameter of about 0.5 nm. X-ray diffraction patterns (XRD), Fourier transform infrared spectra, and simultaneous thermal analysis data (STA) were obtained to confirm the synthesis products.     

Preparation and properties of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanorods as supercapacitor material

Co₃O₄ nanorods have been successfully synthesized by thermal decomposition of the precursor prepared via a facile and efficient microwave-assisted hydrothermal method, using cetyltrimethylammonium bromide (CTAB) with ordered chain structures as soft template for the first time. The obtained Co₃O₄ was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical measurements. The results demonstrate that the as-synthesized nanorods are single crystalline with an average diameter of about 20 to 50 nm and length up to several micrometers. Preliminary electrochemical studies, including cyclic voltammetry (CV), galvanostatic charge–discharge, and electrochemical impedance spectroscopy (EIS) measurements, are carried out in 6 M KOH electrolyte. Specific capacitance of 456 F g⁻¹ for a single electrode could be achieved even after 500 cycles, suggesting its potential application in electrochemical capacitors. This promising method could provide a universal green chemistry approach to synthesize other low-cost and environmentally friendly transition metal hydroxide or oxide.     

Electrical Conductivity of Mullite Ceramics

The electrical conductivity of a lab‐produced homogeneous mullite ceramic sintered at 1625°C for 10 h with low porosity was measured by impedance spectroscopy in the 0.01 Hz to 1MHz frequency range at temperatures between 300°C and 1400°C in air. The electrical conductivity of the mullite ceramic is low at 300°C (≈0.5 × 10^?9 Scm^?1), typical for a ceramic insulator. Up to ≈ 800°C, the conductivity only slightly increases (≈0.5 × 10^?6 Scm^?1 at 800°C) corresponding to a relatively low activation energy (0.68eV) of the process. Above ≈ 800°C, the temperature‐dependent increase in the electrical conductivity is higher (≈10^?5 Scm^?1 at 1400°C), which goes along with a higher activation energy (1.14 eV). The electrical conductivity of the mullite ceramic and its temperature‐dependence are compared with prior studies. The conductivity of polycrystalline mullite is found to lie in‐between those of the strong insulator α‐alumina and the excellent ion conductor Y‐doped zirconia. The electrical conductivity of the mullite ceramic in the low‐temperature field (< ≈800°C) is approximately one order of magnitude higher than that of the mullite single crystals. This difference is essentially attributed to electronic grain‐boundary conductivity in the polycrystalline ceramic material. The electronic grain‐boundary conductivity may be triggered by defects at grain boundaries. At high temperatures, above ≈ 800°C, and up to 1400°C gradually increasing ionic oxygen conductivity dominates.     

ZnO-capped nanorod gas sensors

This paper reports on the synthesis of pristine α-Fe₂O₃ nanorods and Fe₂O₃–ZnO core–shell nanorods using a combination of thermal oxidation and atomic layer deposition (ALD) techniques; the completed nanorods were then used for ethanol sensing studies. The crystal structure and morphology of the synthesized nanostructures were examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The sensing properties of the pristine and core–shell nanorods for gas-phase ethanol were examined using different concentrations of ethanol (5–200 ppm) at different temperatures (150–250 °C). The XRD and SEM revealed the excellent crystallinity of the Fe₂O₃–ZnO core–shell nanorods, as well as their uniformity in terms of shape and size. The Fe₂O₃–ZnO core–shell nanorod sensor showed a stronger response to ethanol than the pristine Fe₂O₃ nanorod sensor. The response (i.e., the relative change in electrical resistance R_a/R_g) of the core–shell nanorod sensor was 22.75 for 100 ppm ethanol at 200 °C whereas that of the pristine nanorod sensor was only 3.85 under the same conditions. Furthermore, under these conditions, the response time of the Fe₂O₃–ZnO core–shell nanorods was 15.96 s, which was shorter than that of the pristine nanorod sensor (22.73 s). The core–shell nanorod sensor showed excellent selectivity to ethanol over other VOC gases. The improved sensing response characteristics of the Fe₂O₃–ZnO core–shell nanorod sensor were attributed to modulation of the conduction channel width and the potential barrier height at the Fe₂O₃–ZnO interface accompanying the adsorption and desorption of ethanol gas as well as to preferential adsorption and diffusion of oxygen and ethanol molecules at the Fe₂O₃–ZnO interface.     

Microstructure and mechanical properties of B4C matrix composites prepared via hot-pressing sintering with Pr6O11 as additive

High-performance B₄C-PrB₆ composites were prepared via hot-pressing sintering with matrix phase B₄C and with 2–5 wt% Pr₆O₁₁ as additive. The effects of different sintering processes and Pr₆O₁₁ content on the microstructure and mechanical properties of the composites were studied in detail. It is found that increasing sintering temperature and pressure will contribute to the densification of B₄C-PrB₆ composites. Coarse grains are formed in B₄C without additives at high temperature conditions, resulting in the decrease of the densification. Pr₆O₁₁ can effectively hinder the formation of coarse grains and finally promote the densification of the composites. The main toughening mechanisms of composites was crack deflection. The composites with 4 wt% Pr₆O₁₁ prepared at 2050 °C and 25 MPa had the best comprehensive mechanical properties. The relative density, hardness, flexural strength and fracture toughness reached to 98.9%, 37.6 GPa, 339 MPa and 4.4 MP am^1/2, respectively.     

Tin Oxide Nanorod Array-Based Electrochemical Hydrogen Peroxide Biosensor

SnO₂ nanorod array grown directly on alloy substrate has been employed as the working electrode of H₂O₂ biosensor. Single-crystalline SnO₂ nanorods provide not only low isoelectric point and enough void spaces for facile horseradish peroxidase (HRP) immobilization but also numerous conductive channels for electron transport to and from current collector; thus, leading to direct electrochemistry of HRP. The nanorod array-based biosensor demonstrates high H₂O₂ sensing performance in terms of excellent sensitivity (379 μA mM⁻¹ cm⁻²), low detection limit (0.2 μM) and high selectivity with the apparent Michaelis–Menten constant estimated to be as small as 33.9 μM. Our work further demonstrates the advantages of ordered array architecture in electrochemical device application and sheds light on the construction of other high-performance enzymatic biosensors.     

Electrochemical investigation of Li–Al anodes in oligo(ethylene glycol) dimethyl ether/LiPF<Subscript>6</Subscript>

1 M LiPF₆ dissolved in oligo(ethylene glycol) dimethyl ether with a molecular weight 500 g mol⁻¹ was investigated as a new electrolyte (OEGDME500, 1 M LiPF₆) for metal deposition and battery applications. At 25 °C a conductivity of 0.48 × 10⁻³ S cm⁻¹ was obtained and at 85 °C, 3.78 × 10⁻³ S cm⁻¹. The apparent activation barrier for ionic transport was evaluated to be 30.7 kJ mol⁻¹. OEGDME500, 1 M LiPF₆ allows operating temperature above 100 °C with very attractive conductivity. The electrolyte shows excellent performance at negative and positive potentials. With this investigation, we report experimental results obtained with aluminum electrodes using this electrolyte. At low current densities lithium ion reduction and re-oxidation can be achieved on aluminum electrodes at potentials about 280 mV more positive than on lithium electrodes. In situ X-ray diffraction measurements collected during electrochemical lithium deposition on aluminum electrodes show that the shift to positive potentials is due to the negative Gibbs free energy change of the Li–Al alloy formation reaction.     

Temperature dependence of electrical conductivity of a green porcelain mixture

AC conductivity of a green porcelain body was investigated using impedance spectroscopy over a temperature range of 100–950 °C. The results showed that during the heating, conductivity at 100–200 °C increased mainly arising from H⁺ and OH⁻ ions generated from adsorbing physical water. The activation energy increased below the dehydroxylation of clay resulting from movement of monovalent ions. At the dehydroxylation of clay, a combination of H⁺, OH⁻ and monovalent ions dominated the conductivity. The activation energy rose to 1.14 eV (600–950 °C) controlled by diffusion of Na⁺, and K⁺ ions. During the cooling, conductivity showed single activation energy with 0.86 eV resulting from denser microstructure and change in mineralogical constituents and the heat treated porcelain sample showed higher electrical conductivity at the same temperature. Understanding conduction behaviour of the green porcelain enabled more accurate control of furnace temperature in flash sintering, a process which relies on electrical conductivity at high temperatures.     

Ethanol sensing properties of networked In2O3 nanorods decorated with Cr2O3-nanoparticles

In₂O₃ nanorods decorated with Cr₂O₃ nanoparticles were synthesized by thermal evaporation of In₂S₃ powder in an oxidizing atmosphere followed by solvothermal deposition of Cr₂O₃ and their ethanol gas sensing properties were examined. The pristine and Cr₂O₃-decorated In₂O₃ nanorods exhibited responses of ~524% and ~1053%, respectively, to 500-ppm ethanol at 200 °C. The Cr₂O₃-decorated In₂O₃ nanorod sensor showed stronger electrical response to ethanol gas at 200 °C than the pristine In₂O₃ nanorod counterpart. The former also showed faster response and recovery than the latter. The pristine and Cr₂O₃-decorated In₂O₃ nanorod sensors showed the strongest response to ethanol gas at 250 and 200 °C, respectively. The Cr₂O₃-decorated In₂O₃ nanorod sensor showed selectivity for ethanol gas over other reducing gases. The underlying mechanism for the enhanced response, sensing speed and selectivity of the Cr₂O₃-decorated In₂O₃ nanorod sensor for ethanol gas is discussed.     

Conjugated opto/electroactive ethynylene-carbazole polymers with TTF as pendant group

Three conjugated ethynylene-carbazole polymers with Tetrathiafulvalene (TTF) as pendant group (P1–P3) were synthesized by using sonogashira coupling reaction and characterized by ¹H NMR, GPC, CV, UV–Vis, FL, and TGA. CV and UV–Vis spectra showed that an intramoleular interaction existed between the electron-rich moiety TTF and electron-deficient moiety polyethynylcarbazole of the polymers. A strong fluorescence quench (ca. 99%) could be observed, compared to the polyethynylene-carbazole without TTF units, which could be ascribed to the photo-induced electron transfer (PET) interaction from TTF moiety to the polyethynylene-carbazole backbone. The observed onset decomposition temperatures (T _d) for P1–P3 varied from 256 to 298 °C. The polymers mentioned above exhibited good thermal properties and higher conductivity (neutral conductivity ~7–11 × 10⁻⁷ S cm⁻¹; doped conductivity ~6–11 × 10⁻⁴ S cm⁻¹).     

Influence of Al2O3 on the electrical conductivity and structure of calcium-silicate-based melts

Electrical conductivity and structure of the CaO-SiO₂-based mold flux melts with various Al₂O₃ contents were investigated. The results show that the electrical conductivity increases with the addition of Al₂O₃ from 2 wt% to 4 wt%, but decreases with the further increase of Al₂O₃ from 4 wt% to 8 wt%. Correspondingly, the apparent activation energy reduces firstly from 55.12 ± 1.20 kJ mol to 41.09± 0.38 kJ mol, and then increases from 41.09 ± 0.38 kJ mol to 98.99 ± 1.42 kJ mol. The structure analyses suggest that complex structural units, such as Si-O-Al, Al-O⁰, Si-O-Si and Q³(Si), reduce first, but increase with the further addition of Al₂O₃. Conversely, these simple structural units, such as Al-O^-, Q⁰(Si), Q¹(Si) and Q²(Si) vary in the opposite way with the change of Al₂O₃ content. From the variations of electrical conductivity, activation energy and structural units, it can be found that when Al₂O₃ works as network breaker to simplify the melt structure, the energy barrier for transportation of conducting ions/ionic reduce, which results in the increase of electrical conductivity; while when Al₂O₃ becomes into network former, the conductivity increases, correspondingly.     

Structural Refinement and Photoluminescence Properties of MnWO4 Nanorods Obtained by Microwave-Hydrothermal Synthesis

Manganese tungstate (MnWO₄) nanorods were prepared at room temperature by the co-precipitation method and synthesized after processing in a microwave-hydrothermal (MH) system at 140 °C for 6–96 min. These nanorods were structurally characterized by X-ray diffraction (XRD), Rietveld refinements and Fourier transform (FT)-Raman spectroscopy. The growth direction, shape and average size distribution of nanorods were observed by means of transmission electron microscopy (TEM) and high resolution TEM (HR-TEM). The optical properties of the nanorods were investigated by ultraviolet visible (UV-vis) absorption and photoluminescence (PL) measurements. XRD patterns, Rietveld refinement data and FT-Raman spectroscopy indicate that the MnWO₄ precipitate is not a single phase structure while the nanorods synthesized by MH processing have a wolframite-type monoclinic structure without deleterious phases. FT-Raman spectra exhibited the presence of 17 Raman-active modes from 50 to 1,000 cm⁻¹. TEM and HR-TEM micrographs indicated that the nanorods are aggregated due to surface energy by Van der Waals forces and grow along the [100] direction. UV–vis absorption measurements confirmed non-linear values for the optical band gap (from 3.2 to 2.72 eV), which increased as the MH processing time increased. The structural characterizations indicated that the presence of defects in the MnWO₄ precipitate promotes a significant contribution to maximum PL emission, while MnWO₄ nanorods obtained by MH processing decrease the PL emission due to the reduction of defects in the lattice.     

Stabilizing the structure and suppressing the voltage decay of Li[Li0.2Mn0.54Co0.13Ni0.13]O2 cathode materials for Li-ion batteries via multifunctional Pr oxide surface modification

The development of Li-rich layer cathode materials has been limited by poor cycle, rate performance, phase transformation and voltage decay. To improve these properties, a facile and low-cost wet method is employed to fabricate Pr₆O₁₁ coating layer on Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ nanoparticles. The 3–6 nm Pr₆O₁₁ coating layer is observed on the surface of Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ by HRTEM. Interestingly, HAADF-STEM and EDS analyses show that the transition metal ions and the praseodymium ions mutually infiltrate in the Pr₆O₁₁ coating layer and Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ nanoparticles during calcination. A combination of HAADF-STEM with EDS and XPS studies reveals that Pr₆O₁₁ coating layer is bridged to Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ nanoparticles by the chemical bonds of transition phase Li_1.2M_XPr_1−xO₂. XRD patterns show that all samples are indexed to the layered structure α-NaFeO₂, but the lattice parameters are influenced lightly after Pr₆O₁₁ coating. HRTEM and SAED analyses elucidate that the super large Pr ions surface-doping and the Pr₆O₁₁ coating are verified to suppress the transformation of layer to spinel structure in the bulk nanoparticles after cycles. The sample coated with 3 wt% Pr₆O₁₁ exhibits wonderful electrochemical performance with the first coulomb efficiency of 85.6%, the capacity retention ratio of 97.9% after 50 cycles and the discharge capacity of 162.2 mAh g⁻¹ at 5 C. The resistant of charge transfer and the electrodes polarization are reduced by Pr₆O₁₁ coating according to EIS. Therefore, Pr₆O₁₁, which contains the super large Pr ions, plays two roles: the first one, it is coated on the Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ nanoparticles to optimize the environment of the interface reaction between electrodes and electrolyte; the other one, its Pr ions surface-doping stabilizes the structure in the superficial region of Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ nanoparticles and suppresses the voltage decay. The multifunctional Pr₆O₁₁ can play a significant role in accelerating development of new materials with excellent stabilization and high capacity.     

Mixed conductivity of garnet phases based on gadolinium ferrite

Incorporation of Pr and Ca into the garnet lattice of Gd₃Fe₅O_12±δ was found to increase the electronic conductivity, and to decrease the thermal expansion coefficients and oxygen ion transference numbers. The ionic conductivity of Gd_2.2Pr_0.8Fe₅O_12±δ ceramics is similar to that of undoped gadolinium ferrite, whilst Gd_2.5Ca_0.5Fe₅O_12-δ exhibits slightly higher ionic transport, suggesting an enhanced vacancy contribution. The activation energies for ionic conduction in Gd₃Fe₅O₁₂-based materials vary in the narrow range 211–224 kJ/mol. Due to a significantly lower activation energy for the total conductivity (24–81 kJ/mol), the oxygen ion transference numbers in air increase with temperature, from 4 × 10⁻⁵ – 5×10⁻³. Steady-state oxygen permeation fluxes through dense garnet membranes are limited by bulk ambipolar conductivity. The thermal expansion coefficients of the ferrite ceramics (100–1000 °C) were found linear and in the range 10.36–10.86 × 10⁻⁶ K⁻¹.     

Electrochemical investigation of Al–Li/Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>FePO<Subscript>4</Subscript> cells in oligo(ethylene glycol) dimethyl ether/LiPF<Subscript>6</Subscript>

1 M LiPF₆ dissolved in oligo(ethylene glycol) dimethyl ether with a molecular weight, 500 g mol⁻¹ (OEGDME500, 1 M LiPF₆), was investigated as an electrolyte in experimental Al–Li/LiFePO₄ cells. More than 60 cycles were achieved using this electrolyte in a Li-ion cell with an Al–Li alloy as an anode sandwiched between two Li _x FePO₄ electrodes (cathodes). Charging efficiencies of 96–100% and energy efficiencies of 86–89% were maintained during 60 cycles at low current densities. A theoretical investigation revealed that the specific energy can be increased up to 15% if conventional LiC₆ anodes are replaced by Al–Li alloy electrodes. The specific energy and the energy density were calculated as a function of the active mass per electrode surface (charge density). The results reveal that for a charge density of 4 mAh cm⁻² about 160 mWh g⁻¹ can be reached with Al–Li/LiFePO₄ batteries. Power limiting diffusion processes are discussed, and the power capability of Al–Li/LiFePO₄ cells was experimentally evaluated using conventional electrolytes.     

Synthesis, structure and magnetic properties of β-MnO 2 nanorods

We present synthesis, structure and magnetic properties of structurally well-ordered single-crystalline β-MnO₂ nanorods of 50–100 nm diameter and several μm length. Thorough structural characterization shows that the basic β-MnO₂ material is covered by a thin surface layer (∼2.5 nm) of α-Mn₂O₃ phase with a reduced Mn valence that adds its own magnetic signal to the total magnetization of the β-MnO₂ nanorods. The relatively complicated temperature-dependent magnetism of the nanorods can be explained in terms of a superposition of bulk magnetic properties of spatially segregated β-MnO₂ and α-Mn₂O₃ constituent phases and the soft ferromagnetism of the thin interface layer between these two phases.     

Tunable ultra-wideband NIR emission and irradiation resistance in novel Er3+/Tm3+/Pr3+ tri-doped La2O3- Ga2O3-Ta2O5 glasses synthesized using aerodynamic levitation method

Glasses with ultra-wideband near-infrared emission and superior irradiation resistance are important for the potential applications in optical communications under harsh environments. Here, transparent 35La₂O₃-(65-x)Ga₂O₃-xTa₂O₅ (LGT) and Er³⁺/Tm³⁺/Pr³⁺ tri-doped LGT glasses are fabricated using the levitation method. LGT glasses exhibit a wide glass-formation region, low largest vibration energy, high refractive indices, and excellent mechanical properties. Additionally, Er³⁺/Tm³⁺/Pr³⁺ tri-doped LGT samples with varying Pr³⁺ contents are characterized by possessing good thermal stability (T_g>849°C), wide transparent optical window, strong radiation resistance, excellent compatibility between low wavelength dispersion (v_d>31.2), and large refractive index (n_d>2.048). By optimizing the doping content of Er³⁺, Tm³⁺, and Pr³⁺ in an appropriate ratio, the ultra-wideband near-infrared luminescence ranging from 1250 to 1640 nm (FWHM = 251 nm) has been acquired under 808 nm pumping. Furthermore, decay curves are measured to reveal the fluorescence dynamics, and then the related emission mechanism is elaborated systematically. Meanwhile, the effects of gamma irradiation doses on microstructure, transmittance spectra, and fluorescence characteristics are studied. This work may offer a valuable reference for doping optimization and new design strategy of multifunctional materials.