Thermal conductivity of Na<Subscript>2</Subscript>W<Subscript>2</Subscript>O<Subscript>7</Subscript> crystal

The thermal conductivity of Na₂W₂O₇ single crystal has been studied along the main crystallographic directions at temperatures of 50–573 K. A low thermal conductivity is found to correlate with a significant difference in the cation weight.     

Synthesis and electrochemical performance of spherical LiNi<Subscript>0.8</Subscript>Co<Subscript>0.15</Subscript>Ti<Subscript>0.05</Subscript>O<Subscript>2</Subscript> cathode materials with high tap density

A series of spherical LiNi_0.8Co_0.15Ti_0.05O₂ cathode materials were synthesized through co-oxidation-controlled crystallization method followed by solid-state reaction at different calcination temperatures under oxygen flowing. The crystal structure and particles morphology of the as-prepared powders were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. All samples correspond to the layered α-NaFeO₂ structure with R-3m space group. The LiNi_0.8Co_0.15Ti_0.05O₂ prepared at 800 °C presents a better hexagonal ordering structure and better spherical particles and possesses a high tap density of 3.22 g cm^?3. Meanwhile, the NCT-2 sample exhibits an advanced electrochemical performance with an initial discharge capacity of 174.2 mAh g^?1 and capacity retention of 86.7 % after 30 cycles at 0.2 C.     

An approach to improve the electrochemical performance of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> at high temperature

In order to overcome the severe capacity decay of LiMn₂O₄ at high temperature, TiN is used as an active materials additive in this paper. The XRD and XPS test results indicate that the TiN can effectively prevent Mn from dissolving in electrolyte; galvanostatic charge-discharge test shows that LiMn₂O₄ electrode with TiN exhibits remarkably improved capacity retention at high temperature with capacity of 105.1 mAh g^?1 at 1 C in the first cycle at 55 °C and the capacity maintains 88.9% retention after 150 cycles. And the electrochemical impedance spectroscopy result demonstrates TiN’s effectiveness in easing the increase of charge-transfer resistance during cycling. Therefore, we can conclude that TiN, as an addictive, made obvious contribution to the greatly improved electrochemical cycling performance of LiMn₂O₄.     

High-temperature heat capacity of stannates Pr<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript> and Nd<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript>

Oxide compounds Pr₂Sn₂O₇ and Nd₂Sn₂O₇ have been obtained by solid-phase synthesis. The effect of temperature on the heat capacity of Pr₂Sn₂O₇ (360–1045 K) and Nd₂Sn₂O₇ (360–1030 K) has been studied using differential scanning calorimetry. The thermodynamic properties of the compounds (changes in enthalpy, entropy, and the reduced Gibbs energy) have been calculated by the experimental data of C_p = f(T).     

First-principle calculations for electronic structure and bonding properties in layered Na<Subscript>2</Subscript>Ti<Subscript>3</Subscript>O<Subscript>7</Subscript>

First-principles calculations of Na₂Ti₃O₇ have been carried out with density-functional theory (DFT) and ultrasoft pseudopotentials. The electronic structure and bonding properties in layered Na₂Ti₃O₇ have been studied through calculating band structure, density of states, electron density, electron density difference and Mulliken bond populations. The calculated results reveal that Na₂Ti₃O₇ is a semiconductor with an indirect gap and exhibits both ionic and covalent characters. The stability of the (Ti₃O₇)²⁻ layers is attributed to the covalent bonding of strong interactions between O 2p and Ti 3d orbitals. Furthermore, the O atoms located in the innerlayers interact more strongly with the neighboring Ti atoms than those in the interlayer regions. The ion-exchange property is due to the ionic bonding between the Na⁺ and (Ti₃O₇)²⁻ layers, which can stabilize the interlayers of layered Na₂Ti₃O₇ structure.     

Synthesis and electrochemical performance of LiFePO<Subscript>4</Subscript>/C cathode materials from Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> for high-power lithium-ion batteries

Carbon-coated olivine-structured LiFePO₄/C composites are synthesized via an efficient and low-cost carbothermal reduction method using Fe₂O₃ as iron source at a relative low temperature (600 °C). The effects of two kinds of carbon sources, inorganic (acetylene black) and organic (sucrose), on the structures, morphologies, and lithium storage properties of LiFePO₄/C are evaluated in details. The particle size and distribution of the carbon-coated LiFePO₄ from sucrose (LiFePO₄/SUC) are more uniform than that obtained from acetylene black (LiFePO₄/AB). Moreover, the LiFePO₄/SUC nanocomposite shows superior electrochemical properties such as high discharge capacity of 156 mAh g^?1 at 0.1 C, excellent cyclic stability, and rate capability (78 mAh g^?1 at 20 C), as compared to LiFePO₄/AB. Cyclic voltammetric test discloses that the Li-ion diffusion, the reversibility of lithium extraction/insertion, and electrical conductivity are significantly improved in LiFePO₄/SUC composite. It is believed that olivine-structured LiFePO₄ decorated with carbon from organic carbon source (sucrose) using Fe₂O₃ is a promising cathode for high-power lithium-ion batteries.     

Synthesis,sintering, and conductivity of Mn<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript>

Studies on the sintering of manganese pyrovanadate depending on the temperature and the crystallite size show that we are prevented from obtaining a bulk ceramic sample by the anisotropic growth of grains. Investigation of the electrical properties of Mn₂V₂O₇ in the temperature range of 250–800°C reveals the activation energy at which bulk conductivity is 0.62 eV.     

Elevated electrochemical property of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> originated from nano-sized Mn<Subscript>3</Subscript>O<Subscript>4</Subscript>

By employment of nano-sized pre-prepared Mn₃O₄ as precursor, LiMn₂O₄ particles have been successfully prepared by facile solid state method and sol-gel route, respectively. And the reaction mechanism of the used precursors of Mn₃O₄ is studied. The structure, morphology, and element distribution of the as-synthesized LiMn₂O₄ samples are characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Compared with LiMn₂O₄ synthesized by facile solid state method (SS-LMO), LiMn₂O₄ synthesized by modified sol-gel route (SG-LMO) possesses higher crystallinity, smaller average particle size (~175 nm), higher lithium chemical diffusion coefficient (1.17 × 10^?11 cm² s^?1), as well as superior electrochemical performance. For example, the cell based on SG-LMO can deliver a capacity of 85.5 mAh g^?1 at a high rate of 5 °C, and manifests 88.3% capacity retention after 100 cycles at 0.5 °C when cycling at 45 °C. The good electrochemical performance of the cell based on SG-LMO is ascribed mainly to its small particle size, high degree of dispersion, and uniform element distribution in bulk material. In addition, the lower polarization potential accelerates Li⁺ ion migration, and the lower atom location confused degree maintains integrity of crystal structure, both of which can effectively improve the rate capability and cyclability of SG-LMO.     

Synthesis and luminescent properties of Eu<Superscript>3+</Superscript>- and Eu<Superscript>2+</Superscript>-activated sodium pyrophosphate Na<Subscript>4</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>

The luminescent properties of Eu³⁺ and Eu²⁺ ions in sodium pyrophosphate, Na₄P₂O₇, have been studied. The excitation spectrum of the Eu³⁺ emission in Na₄P₂O₇ consists of several sets of bands in the range 280–535 nm due to 4f–4f transitions of Eu³⁺ ions and a broad band with a maximum at about 240 nm interpreted to be due to a charge transfer (CT) transition from oxygen 2p states to empty states of the Eu³⁺ 4f⁶-configuration. Although the CT band energy is large enough, the quantum efficiency (η) of the Eu³⁺ emission in Na₄P₂O₇ under CT excitation was estimated to be very low (η ≤ 0.01). In terms of a configurational coordinate model, this fact is interpreted as a result of the high efficiency of a radiationless relaxation from the CT state to the ⁷F₀ ground state of Eu³⁺ ions occupying sodium sites in Na₄P₂O₇. A strong reducing agent is required in order to stabilize Eu²⁺ ions in Na₄P₂O₇ during the synthesis. Several nonequivalent Eu²⁺ luminescence centers in Na₄P₂O₇ were found.     

Synthesis and electrochemical performance of Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C by organic solvent replacement drying method

A series of Li₃V₂(PO₄)₃/C composite cathodes have been prepared by the organic solvent replacement drying method. Five kinds of organic solvent including ethyl alcohol, butyl alcohol, 2-methoxyethanol, 1,2-propylene glycol, and ethylene glycol were used in the drying process to replace the water respectively. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge tests were employed to analyze the crystal structure, morphology, and electrochemical properties of the as-prepared materials. The results show that the organic solvent has a great influence on the secondary particle size of the as-synthesized materials. Special emphasis is placed on the sample prepared with 1,2-propylene glycol, which has the smallest average particle size and uniform distribution, thus leading to the best high rate performance and long-term cycling stability. The electrode exhibits average specific discharge capacities of 127.6, 128.3, 127.7, 126.7, 125.5, 124.4, 121.9, and 117.0 mAh g^?1 at 0.1, 0.2, 0.5, 1, 3, 5, 10, and 20C, respectively. More encouragingly, this sample delivers an outstanding cycle life with capacity retention of up to 94.68% even after 1000 cycles at 20C. Moreover, EIS results demonstrate that this sample has the minimum resistance and the largest apparent lithium ion diffusion coefficient (1.569 × 10^?7 cm² s^?1) which can facilitate to the Li⁺ diffusion during the charge/discharge process. Our results indicate that this preparation strategy can be facile and versatile for the synthesis of other high-rate and high-capacity intercalation materials.     

Synthesis and electrochemical properties of P2-Na<Subscript>2/3</Subscript>Ni<Subscript>1/3</Subscript>Mn<Subscript>2/3</Subscript>O<Subscript>2</Subscript>

The pure phase P2-Na_2/3Ni_1/3Mn_2/3O₂ was synthesized by a solid reaction process. The optimum calcination temperature was 850 °C. The as-prepared product delivered a capacity of 158 mAh g^?1 in the voltage range of 2–4.5 V, and there was a phase transition from P2 to O2 at about 4.2 V in the charge process. The P2 phase exhibited excellent intercalation behavior of Na ions. The reversible capacity is about 88.5 mAh g^?1 at 0.1 C in the voltage range of 2–4 V at room temperature. At an elevated temperature of 55 °C, it could remain as an excellent capacity retention at low current rates. The P2-Na_2/3Ni_1/3Mn_2/3O₂ is a potential cathode material for sodium-ion batteries.     

Preparation and electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/Ti<Subscript>4</Subscript>O<Subscript>7</Subscript> composite for lithium-ion batteries

In order to improve the rate capability of Li₄Ti₅O₁₂, Ti₄O₇ powder was successfully fabricated by improved hydrogen reduction method, then a dual-phase composite Li₄Ti₅O₁₂/Ti₄O₇ has been synthesized as anode material for lithium-ion batteries. It is found that the Li₄Ti₅O₁₂/Ti₄O₇ composite shows higher reversible capacity and better rate capability compared to Li₄Ti₅O₁₂. According to the charge-discharge tests, the Li₄Ti₅O₁₂/Ti₄O₇ composite exhibits excellent rate capability of 172.3 mAh g^?1 at 0.2 C, which is close to the theoretical value of the spinel Li₄Ti₅O₁₂. More impressively, the reversible capacity of Li₄Ti₅O₁₂/Ti₄O₇ composite is 103.1 mAh g^?1 at the current density of 20 C after 100th cycles, and it maintains 84.8% of the initial discharge capacity, whereas that of the bare spinel Li₄Ti₅O₁₂ is only 22.3 mAh g^?1 with a capacity retention of 31.1%. The results indicate that Li₄Ti₅O₁₂/Ti₄O₇ composite could be a promising anode material with relative high capacity and good rate capability for lithium-ion batteries.     

Investigation of the structural and electrochemical performance of Li<Subscript>1.2</Subscript>Ni<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>O<Subscript>2</Subscript> with Cr doping

Cr-doped layered oxides Li[Li_0.2Ni_0.2???x Mn_0.6???x Cr_2x ]O₂ (x?=?0, 0.02, 0.04, 0.06) were synthesized by co-precipitation and high-temperature solid-state reaction. The materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (TRTEM), X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy (EIS). XRD patterns and HRTEM results indicate that the pristine and Cr-doped Li_1.2Ni_0.2Mn_0.6O₂ show the layered phase. The Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂ shows the best electrochemical properties. The first discharge specific capacity of Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂ is 249.6 mA h g^?1 at 0.1 C, while that of Li_1.2Ni_0.2Mn_0.6O₂ is 230.4 mA h g^?1. The capacity retaining ratio of Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂ is 97.9% compared with 93.9% for Li_1.2Ni_0.2Mn_0.6O₂ after 80 cycles at 0.2 C. The discharge capacity of Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂ is 126.2 mA h g^?1 at 5.0 C, while that of the pristine Li_1.2Ni_0.2Mn_0.6O₂ is about 94.5 mA h g^?1. XPS results show that the content of Mn³⁺ in the Li_1.2Ni_0.2Mn_0.6O₂ can be restrained after Cr doping during the cycling, which results in restraining formation of spinel-like structure and better midpoint voltages. The lithium-ion diffusion coefficient and electronic conductivity of Li_1.2Ni_0.2Mn_0.6O₂ are enhanced after Cr doping, which is responsible for the improved rate performance of Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂.     

Synthesis of ZnAl<Subscript>2</Subscript>O<Subscript>4</Subscript>/α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> complex substrates and growth of GaN films

With the solid phase reaction between pulsed-laser-deposited (PLD) ZnO film and α-Al₂O₃ substrate, ZnAl₂O₄/α-Al₂O₃ complex substrates were synthesized. X-ray diffraction (XRD) spectra show that as the reaction proceeds, ZnAl₂O₄ changes from the initial (111)-oriented single crystal to poly-crystal, and then to inadequate (111) orientation. Corresponding scanning electron microscope (SEM) images indicate that the surface morphology of ZnAl₂O₄ transforms from uniform islands to stick structures, and then to bulgy-line structures. In addition, XRD spectra present that ZnAl₂O₄ prepared at low temperature is unstable at the environment of higher temperature. On the as-obtained ZnAl₂O₄/α-Al₂O₃ substrates, GaN films were grown without any nitride buffer using light-radiation heating low-pressure MOCVD (LRH-LP-MOCVD). XRD spectra indicate that GaN film on this kind of complex substrate changes fromc-axis single crystal to poly-crystal as ZnAl₂O₄ layer is thickened. For the single crystal GaN, its full width at half maximum (FWHM) of X-ray rocking curve is 0.4°. Results indicate that islands on thin ZnAl₂O₄ layer can promote nucleation at initial stage of GaN growth, which leads to the (0001)-oriented GaN film.     

Impedance spectroscopy study of Pb<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript> compound

The lead pyrophosphate, Pb₂P₂O₇, compound was prepared by conventional solid-state reaction and identified by X-ray powder diffractometer. Pb₂P₂O₇ has a triclinic structure whose electrical properties were studied using impedance spectroscopy technique. Both impedance and modulus analysis exhibit the grain and grain boundary contribution to the electrical response of the sample. The temperature dependence of the bulk and grain boundary conductivity were found to obey the Arrhenius law with activation energies E _g = 0.66 eV and E _gb = 0.67 eV, respectively. The scaling behavior of the imaginary part of the complex impedance suggests that the relaxation describes the same mechanism at various temperatures.     

Improved structural stability and electrochemical performance of Na<Subscript>3</Subscript>V<Subscript>2</Subscript> (PO<Subscript>4</Subscript>)<Subscript>3</Subscript> cathode material by Cr doping

Cr-doped sodium vanadium phosphate (NVP) in the form of Na₃V_2-xCr_x(PO₄)₃ (x = 0, 0.02, 0.04, 0.08, 0.10) is synthesized via a facile sol-gel route as cathode materials for sodium ion batteries. The structure and morphology of these materials are systematically characterized by x-ray diffraction (XRD), Fourier-infrared spectra (FT-IR), and scanning electron microscope (SEM). XRD analysis reveals that with the increasing amount of Cr, the crystallographic parameters show a descending trend. Electrochemical tests show that the cycle stability and the specific capacity of the sodium ion batteries can be significantly improved by doping Cr into NVP. Among all the Cr-doped cathode materials, Na₃V_1.92Cr_0.08(PO₄)₃ achieves the highest capacity of 112.2 mAh g^?1 and the capacity retention is 97.2 % after 50 cycles. Electrochemical impedance spectroscopy measurements demonstrate that Cr doping is an effective method to reduce the contact resistance of interparticles by suppressing irreversible phase transformation at low sodium contents.     

State of spin glass in SmFeTi<Subscript>2</Subscript>O<Subscript>7</Subscript>

The SmFeTi₂O₇ compound has been synthesized using the solid-phase reaction method. In order to determine the magnetic state, X-ray structural, Mössbauer, calorimetric, and magnetic measurements have been performed. The state of spin glass with the freezing point T _f = 7 K has been found for SmFeTi₂O₇.     

Co<Subscript>3</Subscript>O<Subscript>4</Subscript>@MnO<Subscript>2</Subscript> core shell arrays on nickel foam with excellent electrochemical performance for aqueous asymmetric supercapacitor

At present, a lot of attention has been paid to the reasonable design and synthesis of materials with core shell structure for high-performance supercapacitors. Herein, the Co₃O₄@MnO₂ core shell arrays on nickel foam are successfully synthesized via a facile and effective hydrothermal method followed with annealing process. The sample was characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Electrochemical performance of the Co₃O₄@MnO₂ material was studied using cyclic voltammetry, charge/discharge cycling, and electrochemical impedance measurements in 6 mol L^?1 KOH aqueous electrolyte. The results indicated that the Co₃O₄@MnO₂ material presented excellent electrochemical performance in terms of specific capacitance, cyclic stability, and charge/discharge stability.     

Spherical shape BaO-ZnO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> glass powders prepared by spray pyrolysis

Fine-sized BaO-ZnO-B₂O₃-SiO₂ (BZBS) glass powders were directly prepared by high temperature spray pyrolysis. The hollow glass powders prepared at low preparation temperature of 1000 °C had a low density of 2.65 g/cm³. However, the densities of the BZBS powders obtained at preparation temperatures of 1200 and 1400 °C were each 3.92 and 4.13 g/cm³. The mean size of the BZBS glass powders prepared by spray pyrolysis at preparation temperature of 1400 °C was 0.98 μm. The glass transition temperature (T_g) of the prepared BZBS glass powders was 518.9 °C. The dielectric layers formed from the prepared BZBS glass powders with a dense structure had a clean surface and a dense inner structure without voids at the firing temperature of 580 °C. The transparencies of the dielectric layers formed from the prepared BZBS glass powders were higher than 90% within the visible range. PACS 42.70.Ce; 85.60.Pg; 71.55.Jv