Effect of PbTe on Thermoelectric Properties of Co<Subscript>0.88</Subscript>Ni<Subscript>0.12</Subscript>Sb<Subscript>2.91</Subscript>Sn<Subscript>0.09</Subscript>

The Co_0.88Ni_0.12Sb_2.91Sn_0.09 compound was synthesized by a metallurgical route, and PbTe powder was prepared by the low-temperature aqueous chemical method. Composite materials (xPbTe/Co_0.88Ni_0.12Sb_2.91Sn_0.09) were prepared by the ball-milling and the hot-pressed process. Electrical conductivities of xPbTe/Co_0.88Ni_0.12Sb_2.91Sn_0.09 hot-pressed samples decrease with increase of PbTe content, but their thermal conductivities were effectively improved due to induction of disperse phase. Due to agglomeration of the disperse phase, little thermal conductivity improvement occurs for composite material with low PbTe content. The ZT values of xPbTe/Co_0.88Ni_0.12Sb_2.91Sn_0.09 samples were hardly enhanced due to the negative contribution of electrical conductivity.     

Effects of surface area on electrochemical performance of Li[Ni<Subscript>0.2</Subscript>Li<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>]O<Subscript>2</Subscript> cathode material

The effect of surface area on the electrochemical properties and thermal stability of Li[Ni_0.2Li_0.2Mn_0.6]O₂ powders was characterized using a charge/discharge cycler and DSC (Differential Scanning Calorimeter). The surface area of the samples was successfully controlled from ~4.0 to ~11.7 m² g⁻¹ by changing the molar ratio of the nitrate/acetate sources and adding an organic solvent such as acetic acid or glucose. The discharge capacity and rate capability was almost linearly increased with increase in surface area of the sample powder. A sample with a large surface area of 9.6–11.7 m² g⁻¹ delivered a high discharge capacity of ~250 mAh g⁻¹ at a 0.2 C rate and maintained 62–63% of its capacity at a 6 C rate versus a 0.2 C rate. According to the DSC analysis, heat generation by thermal reaction between the charged electrode and electrolyte was not critically dependent on the surface area. Instead, it was closely related to the type of organic solvent employed in the fabrication process of the powder.     

Voltammetric behavior and the determination of quercetin at a flowerlike Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles modified glassy carbon electrode

Flowerlike Co₃O₄ nanoparticles were used as a modifier on the glassy carbon electrode to fabricate a quercetin (Qu) sensor. The morphology and crystallinity of the prepared Co₃O₄ material were investigated by scanning electron microscopy and X-ray diffraction. Electrochemical behavior of Qu at the sensor was studied by cyclic voltammetry and semi-derivative voltammetry. Results suggested that the modified electrode exhibited a strong electrocatalytic activity toward the redox of Qu. The electron transfer coefficient (α), the number of electron transfer (n), and the diffusion coefficient (D) of Qu at the sensor were calculated. Under the optimum conditions, the catalytic peak currents of Qu were linearly dependent on the concentrations of Qu in the range from 5.0 × 10⁻⁷ to 3.3 × 10⁻⁴ M, with a detection limit of 1.0 × 10⁻⁷ M. This proposed method was successfully applied to determine the quercetin concentration in Ginkgo leaf tablet and human urine samples.     

Proton diffusivity in the BaZr<Subscript>0.9</Subscript>Y<Subscript>0.1</Subscript>O<Subscript>3−δ</Subscript> proton conductor

The thermally activated proton diffusion in BaZr_0.9Y_0.1O_3−δ was studied with electrochemical impedance spectroscopy (IS) and quasi-elastic neutron scattering (QENS) in the temperature range 300–900 K. The diffusivities for the bulk material and the grain boundaries as obtained by IS obey an Arrhenius law with activation energies of 0.46 eV and 1.21 eV, respectively. The activation energies obtained by IS for the bulk are 0.26 eV above 700 K and 0.46 eV, below 700 K. The total diffusivity as obtained by IS is by one order of magnitude lower than the microscopic diffusivity as obtained by QENS. The activation energies obtained by QENS are 0.13 eV above 700 K and 0.04 eV, below 700 K. At about 700 K, the diffusion constants for IS and QENS have a remarkable crossover, suggesting two processes with different activation energies.     

Facile synthesis and high rate capability of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/C composite materials with controllable carbon content

A modified ball-milling-assisted green solid reaction method is provided to prepare Li₄Ti₅O₁₂/C composite materials with controllable carbon content. Thermal analysis was utilized to investigate the reaction process and the temperature for eliminating carbon. The added carbon and the time for eliminating the carbon can affect the particle size and greatly improve the cycling stability and rate performance. Besides, the particle size can reach ~60 nm, the Li₄Ti₅O₁₂ eliminated carbon at 600 °C has ~178% higher discharge capacity than that without added carbon after 500 cycles under the same conditions. As for the Li₄Ti₅O₁₂ with a carbon weight of 10.6%, the second discharge capacity can reach 177.2 and 120.8 mAh g⁻¹ at 1 and 20 C rates, respectively. Its discharge capacity still remains at 118.3 mAh g⁻¹ after 500 cycles under various current rates. The results are comparable to those of the reported Li₄Ti₅O₁₂/PAS composite.     

Preparation and electrochemical performance of Li-rich layered cathode material,Li[Ni<Subscript>0.2</Subscript>Li<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>]O<Subscript>2</Subscript>, for lithium-ion batteries

The Li-rich layered cathode material, Li[Ni_0.2Li_0.2Mn_0.6]O₂, was synthesized via a “mixed oxalate” method, and its structural and electrochemical properties were compared with the same material synthesized by the sol–gel method. X-ray diffraction (XRD) shows that the synthesized powders have a layered O₃–LiCoO₂-type structure with the R-3m symmetry. X-ray photoelectron spectroscopy (XPS) indicates that in the above material, Ni and Mn exist in the oxidation states of +2 and +4, respectively. The layered material exhibits an excellent electrochemical performance. Its discharge capacity increases gradually from the initial value of 228 mA hg⁻¹ to a stable capacity of over 260 mA hg⁻¹ after the 10th cycle. It delivers a larger capacity of 258 mA hg⁻¹ at the 30th cycle. The dQ/dV curves suggest that the increasing capacity results from the redox-reaction of Mn⁴⁺/Mn³⁺.     

Photoelectrochemical characterization of the synthetic crednerite CuMnO<Subscript>2</Subscript>

High quality crednerite CuMnO₂ was prepared by solid state reaction at 950 °C under argon flow. The oxide crystallizes in a monoclinically distorted delafossite structure associated to the static Jahn–Teller (J–T) effect of Mn³⁺ ion. Thermal analysis showed that it converts reversibly to spinel Cu _x Mn_3−x O₄ at ~420 °C in air and further heating reform the crednerite above 940 °C. CuMnO₂ is p-type, narrow semiconductor band gap with a direct optical gap of 1.31 eV. It exhibits a long-term chemical stability in basic medium (KOH 0.5 M), the semi logarithmic plot gave an exchange current density of 0.2 μA cm⁻² and a corrosion potential of ~−0.1 V_SCE. The electrochemical oxygen insertion/desinsertion is evidenced from the intensity–potential characteristics. The flat band potential (V _fb = −0.26 V_SCE) and the holes density (N _A  = 5.12 × 10¹⁸ cm⁻³) were determined, respectively, by extrapolating the curve C ⁻² versus the potential to the intersection with C ⁻²  = 0 and from the slope of the Mott–Schottky plot. From photoelectrochemical measurements, the valence band formed from Cu-3d wave function is positioned at 5.24 ± 0.02 eV below vacuum. The Nyquist representation shows straight line in the high frequency range with an angle of 65° ascribed to Warburg impedance originating from oxygen intercalation and compatible with a system under mass transfer control. The electrochemical junction is modeled by an equivalent electrical circuit thanks to the Randles model.     

Fabrication and Magnetic Properties of Fe<Subscript>65</Subscript>Co<Subscript>35</Subscript>–ZnO Nano-Granular Films

A series of nano-granular films composed of magnetic metal (Fe₆₅Co₃₅) granules with a few nanometers in size and semiconductor oxide (ZnO) have been fabricated by a magnetron sputtering method, and excellent soft magnetic properties have been achieved in a wide metal volume fraction (x) range for as-deposited samples due to the exchange coupling between FeCo granules (a ferromagnetic interaction in nano-scale). In a wide range (0.53 < x < 0.71), the films exhibit coercivity H _C not exceeding 15 Oe, along with high resistivity. Especially for the sample with x = 0.67, coercivities in hard and easy axes are 1.43 and 7.08 Oe, respectively, 4πM _S  = 9.85 kg, and ρ reaches 2.06 × 10³ μΩ cm. The dependence of complex permeability μ = μ′ − jμ″ on frequency shows that the real part μ′ is more than 100 below 1.83 GHz and that the ferromagnetic resonance frequency reaches 2.31 GHz, implying the promising for high frequency application. The measured negative temperature coefficient of resistivity reveals that may be the weak localized electrons existing in samples mediate the exchange coupling.     

Influence of Cobalt Doping on the Physical Properties of Zn<Subscript>0.9</Subscript>Cd<Subscript>0.1</Subscript>S Nanoparticles

Zn_0.9Cd_0.1S nanoparticles doped with 0.005–0.24 M cobalt have been prepared by co-precipitation technique in ice bath at 280 K. For the cobalt concentration >0.18 M, XRD pattern shows unidentified phases along with Zn_0.9Cd_0.1S sphalerite phase. For low cobalt concentration (≤0.05 M) particle size, d _XRD is ~3.5 nm, while for high cobalt concentration (>0.05 M) particle size decreases abruptly (~2 nm) as detected by XRD. However, TEM analysis shows the similar particle size (~3.5 nm) irrespective of the cobalt concentration. Local strain in the alloyed nanoparticles with cobalt concentration of 0.18 M increases ~46% in comparison to that of 0.05 M. Direct to indirect energy band-gap transition is obtained when cobalt concentration goes beyond 0.05 M. A red shift in energy band gap is also observed for both the cases. Nanoparticles with low cobalt concentrations were found to have paramagnetic nature with no antiferromagnetic coupling. A negative Curie–Weiss temperature of −75 K with antiferromagnetic coupling was obtained for the high cobalt concentration.     

Figure of merit enhancement in thermoelectric materials based on γ-Ln0.8Yb0.2S1.5-y (Ln = Gd,Dy) solid solutions

Here we report the study temperature dependencies of the Seebeck coefficient, the electrical resistivity (T = 300–750 K), the total thermal conductivity (T = 300–973 K), and the thermoelectric figure of merit (T = 300–750 K) of ceramic samples of γ-Ln_0.8Yb_0.2S_1.5-y (Ln = Gd, Dy) solid solutions. It was found that Yb³⁺ ions in γ-Ln_0.8Yb_0.2S_1.5-y act as the promoters of higher crystallite nucleation rate during the formation of solid solutions. This results in the sample dispersion increase and the formation of the additional phonon scattering centers (dislocations and strain stresses along the crystallites semi-coherent boundaries). These features of the real structure determined the low value of thermal conductivity of γ-Ln_0.8Yb_0.2S_1.5-y solid solutions. The lowest electrical resistivity 20 μΩ m at 750 K and the thermal conductivity 0.58 W/m K at 973 K, the highest Seebeck coefficient 125 μV/K at 700 K and the maximum thermoelectric efficiency, ZT = 0.60 (at 770 K) were obtained for γ-Dy_0.8Yb_0.2S_1.5-y.     

Influence of composition and temperature on the band gap of glassy melts As<Subscript>2</Subscript>S<Subscript>3</Subscript>-Sb<Subscript>2</Subscript>S<Subscript>3</Subscript>

The edge absorption of glassy melts of the As-Sb-S system are investigated in the temperature interval 77–300 K. It is shown that the temperature dependence of the fundamental absorption edge is described by an exponential function of the photon energy. The temperature and concentration dependences of the optical band gap of glasses of the (As₂S₃)_{100 − x} · (Sb₂S₃) _x section are found. The known Varshni relation is used to describe the temperature dependence.     

Enhancing the thermoelectric performance of CoSb3-based skutterudite by decoupling the electrical and thermal properties by embedding Cu nanoparticles

Co_0.91Ni_0.09Sb₃ embedded with Cu nanoparticles (NPs) was synthesized by applying a hydrothermal process followed by spark plasma sintering. The effects of Cu NPs on the electrical and thermal transport properties of the Co_0.91Ni_0.09Sb₃ matrix were investigated in the temperature range of 303–773 K. Cu NPs introduced into the Co_0.91Ni_0.09Sb₃ matrix slightly decreased the electrical conductivity and significantly enhanced the Seebeck coefficient by the energy filtering effect, leading to an improved power factor at 773 K. Furthermore, a significant decrease in the thermal conductivity was realized by increasing the number of grain boundaries. These favorable effects contributed to the improvement in ZT to a value ~57% higher than that of pristine Co_0.91Ni_0.09Sb₃. The highest ZT value of 1.02 was achieved by incorporating 4.5 wt% of Cu NPs in Co_0.91Ni_0.09Sb₃ at 773 K. Thus, decoupling the electrical and thermal transport properties of thermoelectric materials is a viable strategy for optimizing the ZT value.     

Synthesis of Ni(OH)<Subscript>2</Subscript> nanostructures by the hydrothermal treatment in the presence of guanidine carbonate and their electrochemical properties

Nanostructure control of β-Ni(OH)₂ was attempted by adopting hydrothermal treatment for the high specific surface area (high-SSA) β-Ni(OH)₂ in the presence of guanidine carbonate. β-Ni(OH)₂ nanosheets-linked structures could be synthesized from high-SSA β-Ni(OH)₂ owing to the strong effects of guanidine carbonate for keeping or enlarging SSA during hydrothermal treatment. The discharging capacities of the high-SSA sample showed the highest capacity above 80 % at 0.2C. However, the capacities were decreased with decreasing SSA of the β-Ni(OH)₂ prepared. It was also found that, at lower SSA, charging/discharging rates below 1C did not affect the discharging capacity, i.e., the almost same capacities for 0.2C and 1C. Cyclic voltammetry revealed that the electrochemical reactions for the charging/discharging were considered to be reversible and smooth at various scanning rates. The rate-determining step of the electrochemical reaction is considered to be regulated by the diffusion of the active species involved for the lower SSA samples. However, for the higher SSA sample (280 m² g⁻¹) obtained at 200 °C in the presence of 1.0 × 10⁻¹ mol L⁻¹ guanidine carbonate strongly indicates the effects of the rate of surface reaction or electronic conductivity on rate-determining step of charging/discharging of the material.     

Oxygen permeability and structural stability of La<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>Co<Subscript>0.2</Subscript>Fe<Subscript>0.8</Subscript>O<Subscript>3−<Emphasis Type="Italic">δ</Emphasis></Subscript> membrane

La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ oxides were synthesized by citrate method and hydrothermal method. The oxides prepared by citrate method are perovskite type structure, while the oxides by hydrothermal method have a small amount of secondary phase in the powder. Pyrex glass seal and Ag melting seal provided reliable gas-tight sealing of disk type dense membrane in the range of operation temperature, but commercial ceramic binder could not be removed from the support tube without damage to the tube or membrane. Though the degree of gas tightness increases in the order of glass>Ag>ceramic binder, in the case of glass seal, the undesired spreading of glass leads to an interfacial reaction between it and the membrane and reduction of effective permeation area. The oxygen flux of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ membrane increases with increasing temperature and decreasing thickness, and the oxygen permeation flux through 1.0 mm membrane exposed to flowing air (P _h =0.21 atm) and helium (P₁=0.037 atm) is ca. 0.33 ml/cm²·min at 950 °C. X-ray diffraction analysis for the membrane after permeation test over 160 h revealed that La₂O₃ and unknown compound were formed on the surface of membrane. The segregation compounds of surface elements formed on both surfaces of membrane irrespective of spreading of glass sealing material. This paper was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Thermoelectric properties of Cu-dispersed bi<Subscript>0.5</Subscript>sb<Subscript>1.5</Subscript>te<Subscript>3</Subscript>

A novel and simple approach was used to disperse Cu nanoparticles uniformly in the Bi_0.5Sb_1.5Te₃ matrix, and the thermoelectric properties were evaluated for the Cu-dispersed Bi_0.5Sb_1.5Te₃. Polycrystalline Bi_0.5Sb_1.5Te₃ powder prepared by encapsulated melting and grinding was dry-mixed with Cu(OAc)₂ powder. After Cu(OAc)₂ decomposition, the Cu-dispersed Bi_0.5Sb_1.5Te₃ was hot-pressed. Cu nanoparticles were well-dispersed in the Bi_0.5Sb_1.5Te₃ matrix and acted as effective phonon scattering centers. The electrical conductivity increased systematically with increasing level of Cu nanoparticle dispersion. All specimens had a positive Seebeck coefficient, which confirmed that the electrical charge was transported mainly by holes. The thermoelectric figure of merit was enhanced remarkably over a wide temperature range of 323-523 K.     

Study of electrochemical properties and the charge/discharge mechanism for Li<Subscript>4</Subscript>Mn<Subscript>5</Subscript>O<Subscript>12</Subscript>/MnO<Subscript>2</Subscript>-AC hybrid supercapacitor

Spinel Li₄Mn₅O₁₂ was prepared by a sol–gel method. The manganese oxide and activated carbon composite (MnO₂-AC) were prepared by a method in which KMnO₄ was reduced by activated carbon (AC). The products were characterized by XRD and FTIR. The hybrid supercapacitor was fabricated with Li₄Mn₅O₁₂ and MnO₂-AC, which were used as materials of the two electrodes. The pseudocapacitance performance of the Li₄Mn₅O₁₂/MnO₂-AC hybrid supercapacitor was studied in various aqueous electrolytes. Electrochemical properties of the Li₄Mn₅O₁₂/MnO₂-AC hybrid supercapacitor were studied by using cyclic voltammetry, electrochemical impedance measurement, and galvanostatic charge/discharge tests. The results show that the hybrid supercapacitor has electrochemical capacitance performance. The charge/discharge test showed that the specific capacitance of 51.3 F g⁻¹ was obtained within potential range of 0–1.3 V at a charge/discharge current density of 100 mA g⁻¹ in 1 mol L⁻¹ Li₂SO₄ solution. The charge/discharge mechanism of Li₄Mn₅O₁₂ and MnO₂-AC was discussed.     

Synthesis and characterization of Ni–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composite coatings containing different forms of alumina

Electrodeposited Ni–Al₂O₃ composite coatings were prepared using alumina powders synthesized from solution combustion method, precipitation method and a commercial source. Solution combustion synthesized alumina powder yielded α-phase; precipitation method yielded purely γ-phase; commercial alumina powder was a mixture of α-, δ- and γ-phases. A nickel sulfamate bath was used for electro-codeposition. The current densities (0.23 A dm⁻² for 20 h, 0.77 A dm⁻² for 6 h, 1.55 A dm⁻² for 3 h and 3.1 A dm⁻² for 1.5 h) and bath agitation speeds (100, 200, 600 and 1000 rpm) were varied. The pH variations of the bath were higher during the electrodeposition of combustion synthesized alumina. The effect of different forms of alumina particles on the microhardness and microstructure of the nickel composite coating was studied. Composite coating containing combustion synthesized alumina particles was found to have higher microhardness (550 HK). It was found that at lower agitation speed (100 rpm), bigger particles were incorporated and at higher agitation speed (1000 rpm), smaller particles were incorporated. The area fraction of alumina particles incorporated in nickel matrix was highest for commercial alumina (24%). This study shows that it is not suffice to take just the current density and stirring speeds into account to explain the properties of the coatings but also to take into account the source of particles and their properties.     

Synthesis and electrochemical evaluation of carbon coated Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript> alloy-graphite composite lithium battery anodes

With a view to minimize the unavoidable large volume changes of tin based Cu₆Sn₅ alloy anodes, a composite Cu₆Sn₅/graphite anode has been prepared via. a mechanical alloying process and subsequently coated with disordered carbon through pyrolysis of PVC. Phase pure products with better crystallinity and preferred surface morphology were obtained, as evident from PXRD and SEM respectively. Upon electrochemical charge-discharge, the intermetallic Cu₆Sn₅ alloy-graphite composite anode was found to exhibit an enhanced initial discharge capacity of 564 mAh g⁻¹ followed by significant capacity fade (>20%) especially after five cycles. On the other hand, carbon coated Cu₆Sn₅ alloy-graphite composite demonstrated promising electrochemical properties such as steady reversible capacity (∼200 mAh g⁻¹), excellent cycle performance (<5% capacity fade) and high coulombic efficiency (∼98%) via. significant reduction of volume changes. The carbon coating offers buffering and conductive actions on the anode active material and thereby enhances the electrochemical behavior of carbon coated Cu₆Sn₅ alloy/graphite composite anode material.     

Determination of hydrogenation ability and exchange current of H<Subscript>2</Subscript>O/H<Subscript>2</Subscript> system on hydrogen-absorbing metal alloys

A detailed analysis of potential versus time measurements at galvanostatic charge/discharge conditions (external current change from −1 to +1 mA cm⁻²) for two La–Ni alloys in Ar-saturated 0.1 M KOH solution is presented. It is shown that passivation of the electrodes does not affect the potential jump as a result of current switching over. The value of potential jump allows to calculate the exchange current density for H₂O/H₂ system on the tested material. Anodic potential of the hydrogenated electrode (at i _a = const) linearly increases with logarithm of time which allows to evaluate precisely time necessary for oxidation of hydrogen absorbed during cathodic charging. The method described enables to determine effectiveness of hydrogen absorption by materials applied for negative electrodes of NiMH batteries.     

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.