Transport properties on Sn-filled and Te-doped CoSb<Subscript>3</Subscript> skutterudites

Sn-filled and Te-doped CoSb₃ skutterudites (Sn_xCo₈Sb_23.25Te_0.75) were synthesized by the encapsulated induction melting process. Single δ-phase was successfully obtained by subsequent heat treatment at 823 K for 6 days. Structural characterizations were carried out through X-ray diffraction studies. Transport properties such as the Seebeck coefficient, electrical resistivity, thermal conductivity, carrier concentration and mobility were measured and analyzed. The unfilled Co₈Sb_23.25Te_0.75 sample showed n-type conductivity from 300 K to 700K. However, the Sn-filled Sn_xCo₈Sb_23.25Te_0.75 showed n-type conductivity for z=0.25 and 0.5, and p-type conductivity for z=1.0 and 1.5 from 300 K to 700 K. Thermal conductivity was reduced by the impurity-phonon scattering. The dimensionless figure of merit (ZT) was remarkably improved over that of untreated CoSb₃. However, the ZT value decreased when filling with z≥1.0 because the conductivity type was changed from n-type to p-type, thereby allowing bipolar conduction. The details are discussed in terms of the two-band model and the bipolar thermoelectric effect.     

Structure and magnetic properties of mechanically alloyed Tb0.2Pr0.8（Fe0.4Co0.6）1.93 and magnetostriction of its epoxy composite

The C15 Laves phase with composition Tb_0.2Pr_0.8(Fe_0.4Co_0.6)_1.93 was synthesized by mechanical alloying (MA) and subsequent annealing process. The structure and magnetic properties of Tb_0.2Pr_0.8(Fe_0.4Co_0.6)_1.93 were investigated by means of X-ray diffraction (XRD), a vibrating sample magnetometer, and a standard strain technique. The effect of annealing on the structure and magnetic properties was studied. The analysis of XRD shows that the high Pr-content Tb_0.2Pr_0.8(Fe_0.4Co_0.6)_1.93 alloy with the single phase of MgCu₂-type structure can be successfully synthesized by MA method. The sample annealed at 450°C is found to have a coercivity of 196 kA/m at room temperature. An epoxy/Tb_0.2Pr_0.8(Fe_0.4Co_0.6)_1.93 composite was produced by a cold isostatic pressing technique. A large magnetostriction of 400 ppm, at an applied magnetic field of 800 kA/m, was found for the composite. The epoxy-bonded Tb_0.2Pr_0.8(Fe_0.4Co_0.6)_1.93 composite combines a high magnetostriction with a significant coercivity, which is a promising magnetostrictive material.     

Influence of Sb<Subscript>2</Subscript>O<Subscript>3</Subscript> doping on the properties of KBT-NBT-BT lead-free piezoelectric ceramics

0.144(K0.5Bi0.5)TiO3-0.85(Na0.5Bi0.5)TiO3-0.006BaTiO3(KBT-NBT-BT) lead-free piezoelectric ceramics were prepared using a conventional solid state method.The influence of Sb2O3 doping on the crystal phase,surface microstructure and properties of the KBT-NBT-BT lead-free piezoelectric ceramics were investigated using X-ray diffraction(XRD),scanning electron microscope(SEM) and other analytical methods.The results show that all compositions are of pure perovskite structure solid states.Sb2O3 doping does not influence the microstructure of KBT-NBT-BT lead-free piezoelectric ceramics obviously in the Sb2O3 doping range of 0.1-0.5 wt.%.Sb2O3 functions as a donor when doped small amount,while functions as a acceptor when doped large amount.The piezoelectric strain constant(d33) increases first and then decreases;the dielectric constant(ε3T3/ε0) and the dielectric loss(tanδ) decrease continuously when the amount of Sb2O3 dopant increases.When the doping amount of Sb2O3 is 0.1 wt.%,the KBT-NBT-BT piezoelectric ceramics with good comprehensive properties are obtained,whose d33,ε3T3/ε0 and tanδ are 147 pC/N,1510 and 4.2%,respectively.     

Thermoelectric properties of In<Subscript>z</Subscript>Co<Subscript>4</Subscript>Sb<Subscript>12</Subscript> skutterudites

In this study, indium-filled CoSb₃ skutterudite is synthesized via encapsulated induction melting and subsequent annealing at 823 K for six days, and the crystal structure, lattice constant, filler position, phase homogeneity and stability were investigated. All of the In-filled CoSb₃ samples were n-type conducting samples. The temperature dependence of the electrical resistivity showed In_zCo₄Sb₁₂ is a highly degenerate semiconducting material. The thermal conductivity was reduced considerably by In filling. The highest thermoelectric figure of merit value was achieved when the In filling fraction is 0.25. It was found that the ZT of the In-filled CoSb₃ (In_zCo₄Sb₁₂) was higher than that of the In-substituted CoSb₃ (Co_3.75In_0.25Sb₁₂ and Co₄Sb_11.75In_0.25). This is mainly due to the lower thermal conductivity and higher Seebeck coefficient.     

Enhancement of room-temperature magnetoresistance in La<Subscript>0.6</Subscript>Dy<Subscript>0.1</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript>/Ag<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

The samples of La0.6Dy0.1Sr0.3MnO3/(Ag2O)x/2(x = 0.00, 0.02, 0.04, 0.06, 0.08, 0.10, 0.20, 0.25, and 0.30) were prepared by using the solid-state reaction method.Their magnetic property, transport behavior, transport mechanism and magnetoresistance effect were studied through the measurements of magnetization-temperature(M-T) curves, ρ-T curves and the fitting of ρ-T curves.The results indicated that Ag could take part in the reaction when the doping amount is small.However, when the doping amount is compar...     

The Microstructure and Thermoelectric Properties of Yb-Filled Skutterudite Yb<Subscript>0.1</Subscript>Co<Subscript>4</Subscript>Sb<Subscript>12</Subscript> Under Cyclic Thermal Loading

This paper is devoted to investigating the microstructure and thermoelectric properties of Yb-filled skutterudite Yb_0.1Co₄Sb₁₂ under a cyclic thermal loading from room temperature to 773 K. The results indicate after 1000 cycles, the surface morphology changes dramatically, and clear grain boundaries appear on the surface of the sample. The grain sizes of the sample change little after 1000 cycles, and the main phase is still skutterudite; however, a trace amount of YbSb also exists. In addition, the electrical conductivity and thermal conductivity decrease distinctly after 1000 cycles, but the absolute value of the Seebeck coefficient increases a little. Consequently, the ZT value decreases slightly from 0.75 at 800 K before cycling to 0.69 after 1000 cycles. It indicates that the effect of the cyclic thermal loading on the ZT of the Yb_0.1Co₄Sb₁₂ material is not distinct.     

Thermoelectric properties of n-type Bi<Subscript>2</Subscript>Te<Subscript>2.7</Subscript>Se<Subscript>0.3</Subscript> compounds prepared by spark plasma sintering

In this study, the thermoelectric properties of 0.1 wt.% Cdl₂-doped n-type Bi₂Te_2.7Sb_0.3 compounds, fabrieated by SPS in a temperature range of 250°C to 350°C, were characterized. The density of the compounds was increased to approximately 100% of the theoretical density by carrying out consolidation at 350°C. The Seebeck coefficient, thermal conductivity, and electrical resistivity were dependent on a hydrogen reduction process and the sintering temperature. The Seebeck coefficient and the electrical resistivity increased with the reduction process. Also, electrical resistivity decreased and thermal conductivity increased with sintering temperature. The results suggest that carrier density and mobility vary according to the reduction process and sintering temperature. The highest figure of merit, 1.93×10⁻³ K⁻¹, was obtained for the compound consolidated at 350°C for 2 min.     

Effect of NiFe<Subscript>2</Subscript>O<Subscript>4</Subscript> doping on the structure,magnetic properties and electrical properties of La<Subscript>0.7</Subscript>Ca<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript>

The (La_0.7Ca_0.3MnO₃)_1x /(NiFe₂O₄) _x (x = 0 to 0.09) composites were prepared using a conventional solid state reaction method. The structural, magnetic properties, and electrical properties of LCMO/NFO composites were investigated using X-ray diffraction, scanning electron microscopy, field cooled DC magnetization, and magnetoresistance (MR) measurements. The resistivity measured as a function temperature demonstrates that the pure LCMO and x = 0.01 samples display metal to semiconductor transitions. However, the composites of x > 0.03 samples clearly present the electrical behavior as an insulator/semiconductor type behavior. It was observed that the resistivity of the samples increased systemically with an increase of the NFO content. From the MR measurements, it was found that the MR effect is enhanced for x = 0.01 with a NFO composition. In all, the spin-polarized tunneling and the spin-dependent scattering may be beneficial for an improved low-field magnetoresistance effect. These phenomena can be explained by the segregation of a new phase related to NFO at the grain boundaries or surfaces of the LCMO grains.     

Preparation and properties of a nano TiO<Subscript>2</Subscript>/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> composite superparamagnetic photocatalyst

Nano TiO₂/Fe₃O₄ composite particles with different molar ratios of TiO₂ to Fe₃O₄ were prepared via sol-gel method. X-ray diffraction, transmission electron microscopy, and vibration sample magnetometry were used to characterize the TiO₂/Fe₃O₄ particles. The photocatalytic activity of the particles was tested by degrading methyl blue solution under UV illumination (254 nm). The results indicate that with the content of TiO₂ increasing, the photocatalytic activity of the composite particles enhances, while the magnetism of the particles decreases. When the molar ratio of TiO₂ to Fe₃O₄ is about 8, both the photocatalytic activity and magnetism of the TiO₂/Fe₃O₄ particles are relatively high, and their photocatalytic activity remains well after repeated use.     

Magnetocaloric effect of （Gd1-xCex）Co2 compounds in low magnetic fields

The phases in the compounds (Gd_1−x Ce _x )Co₂ with x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5 were investigated by X-ray diffraction, and the magnetocaloric effect for x = 0–0.4 was studied by magnetization measurements. The samples are almost single phase with a cubic MgCu₂-type structure for x = 0–0.5. The magnetization decreases with an increase in Ce content. There is almost no magnetic transition for x = 0.5 at 100–350 K. The Curie temperature (T _c) of the (Gd_1−x Ce _x )Co₂ compounds with x from 0.1 to 0.4 are 350, 344, 340, and 338 K respectively. The maximum magnetic entropy change is 2.34 J·kg⁻¹·K⁻¹ when x = 0.3. The results of Arrott plots show that the magnetic phase transition is second-order magnetic phase transition in these compounds.     

Phase Equilibria in the Tl<Subscript>2</Subscript>Te-Tl<Subscript>5</Subscript>Te<Subscript>3</Subscript>-Tl<Subscript>9</Subscript>TmTe<Subscript>6</Subscript> Section of the Tl-Tm-Te System

Phase equilibria in the Tl₂Te-Tl₅Te₃-Tl₉TmTe₆ section of the Tl-Tm-Te ternary system were experimentally studied by using the powder x-ray diffraction technique, differential thermal analysis, as well as microhardness measurements applied to equilibrated alloys. Several isopleth sections and isothermal section at 680 K, as well as projections of the liquidus and solidus surfaces, were constructed. The Tl₅Te₃-Tl₉TmTe₆ section is characterized by the formation of continuous series of solid solutions (δ-phase) with Tl₅Te₃ tetragonal structure, which penetrate deep into the concentration triangle and occupy more than 90% of its area. A narrow area of solid solutions (α-phase) based on Tl₂Te was detected.     

Synthesis and characterization of Li<Subscript>1.3</Subscript>Al<Subscript>0.3</Subscript>Ti<Subscript>1.7</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-coated LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> by wet chemical route

Li_1.3Al_0.3Ti_1.7(PO₄)₃-coated LiMn₂O₄ was prepared by wet chemical route. The phase, surface morphology, and electrochemical properties of the prepared powders were characterized by X-ray diffraction, scanning electron micrograph, and galvanostatic charge-discharge experiments. Li_1.3Al_0.3Ti_1.7(PO₄)₃-coated LiMn₂O₄ has similar X-ray diffraction patterns as LiMn₂O₄. The corner and border of Li_1.3Al_0.3Ti_1.7(PO₄)₃-coated LiMn₂O₄ particles are not as clear as the uncoated one. The two powders show similar values of lithium-ion diffusion coefficient. When cycled at room temperature and 55°C for 40 times at the charge-discharge rate of 0.2C, Li_1.3Al_0.3Ti_1.7(PO₄)₃-coated LiMn₂O₄ shows the capacity retentions of 98.2% and 93.9%, respectively, which are considerably higher than the values of 85.4% and 79.1% for the uncoated one. Both the capacity retention differences between Li_1.3Al_0.3Ti_1.7(PO₄)₃-coated LiMn₂O₄ and LiMn₂O₄ cycling at room temperature and 55°C become larger with the increase of charge-discharge rate. When the charge-discharge rate reaches 2C, the capacity retention of LATP-coated LiMn₂O₄ becomes 8.4% higher than the uncoated LiMn₂O₄ for room temperature cycling, and it becomes 11.1% higher than the latter when cycled at 55°C.     

Mechanism for the degradation of MmNi<Subscript>3.9</Subscript>Co<Subscript>0.6</Subscript>Mn<Subscript>0.3</Subscript>Al<Subscript>0.2</Subscript> electrode and effects of additives on electrode degradation for Ni-MH secondary batteries

Electrode degradation can affect the lifetime and safety of Ni-MH secondary batteries. This study examined the factors responsible for the degradation of metal hydride (MH) electrodes. The charge-discharge characteristics and cycle life of an MmNi_3.9Co_0.6Mn_0.3Al_0.2 (Mm: misch metal) type MH electrode were examined in a cell with a KOH electrolyte. After the charge-discharge cycles, the surface morphology of the electrodes was analyzed to monitor the extent of degradation. Electrochemical impedance spectroscopy provided information on the conductivity of the electrode. X-ray photon spectroscopy (XPS) was used to quantify the degradation of the electrode in terms of its composition. The MH electrodes degraded with cycling. This phenomenon was more prominent at higher C-rates and temperatures. The electrode degradation was attributed to the loss of active material from the current collector by the repeated absorption and desorption of hydrogen and the formation of an Al₂O₃ oxide layer on the electrode surface with cycling. In addition, the effects of the addition of Co nano and Y₂O₃ powder on the degradation of the MmNi_3.9Co_0.6Mn_0.3Al_0.2 electrode were examined. The addition of the Y₂O₃ and Co nano powder significantly improved the performance of the MH electrode by increasing the cycle life and initial activation rate.     

Electromagnetic wave absorbing properties of Fe<Subscript>73</Subscript>Si<Subscript>16</Subscript>B<Subscript>7</Subscript>Nb<Subscript>3</Subscript>Cu<Subscript>1</Subscript> base P/M sheets mixed with dielectric fine particles

Fe-based nanocrystalline powder sheets with dielectric TiO₂ powder additives were investigated to improve the characteristics of electromagnetic (EM) wave absorption. The amorphous ribbons of Fe₇₃Si₁₆B₇Nb₃Cu₁ (at.%) alloys were prepared by a planar flow casting (PFC) process, and the ribbons were pulverized using an attrition mill. Fe-based flake powder crystallized at 550°C for 1h was mixed with a nano-sized and a micro-sized TiO₂ powder. The powder mixtures were then tape-cast with binders to become EM wave-absorbing sheets. The absorbing properties of the fabricated sheet sample, such as complex permittivity and permeability, were measured by a network analyzer. The properties of EM wave absorption improved with the increase of TiO₂ powder in the mixture. The mixture with micro-sized TiO₂ powder was a little more effective in causing power loss of EM waves than the mixture with nano-sized TiO₂ powder.     

Surface modification of LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> with Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> for lithium ion batteries

Cr 2 O 3-coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 cathode materials were synthesized by a novel method. The structure and electrochemical properties of prepared cathode materials were measured using X-ray diffraction (XRD), scanning electron microscopy (SEM), charge-discharge tests, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The measured results indicate that surface coating with 1.0 wt% Cr 2 O 3 does not affect the LiNi 1/3 Co 1/3 Mn 1/3 O 2 crystal structure (α-NaFeO 2 ) of the cathode material compared to the pristine material, the surfaces of LiNi 1/3 Co 1/3 Mn 1/3 O 2 samples are covered with Cr 2 O 3 well, and the LiNi 1/3 Co 1/3 Mn 1/3 O 2 material coated with Cr 2 O 3 has better electrochemical performance under a high cutoff voltage of 4.5 V. Moreover, at room temperature, the initial discharging capacity of LiNi 1/3 Co 1/3 Mn 1/3 O 2 material coated with 1.0 wt.% Cr 2 O 3 at 0.5C reaches 169 mAh·g 1 and the capacity retention is 83.1% after 30 cycles, while that of the bare LiNi 1/3 Co 1/3 Mn 1/3 O 2 is only 160.8 mAh·g 1 and 72.5%. Finally, the coated samples are found to display the improved electrochemical performance, which is mainly attributed to the suppression of the charge-transfer resistance at the interface between the cathode and the electrolyte.     

Photoresponse and donor concentration of plasma-sprayed TiO<Subscript>2</Subscript> and TiO<Subscript>2</Subscript>-ZnO electrodes

The photoelectrochemical characteristics of plasma-sprayed porous TiO₂, TiO₂-5%ZnO, and TiO₂-10%ZnO electrodes in 0.1 N NaOH solution were studied through a three-electrode cell system. The microstructure, morphology, and composition of the electrodes were analyzed using an electron probe surface roughness analyzer (ERA-8800FE), scanning electron microscopy, and x-ray diffraction. The results indicate that the sprayed electrodes have a porous microstructure, which is affected by the plasma spray parameters and composition of the powders. The TiO₂-ZnO electrodes consist of anatase TiO₂, rutile TiO₂, and Zn₂Ti₃O₈ phase. The photoresponse characteristics of the plasma-sprayed electrodes are comparable to those of single-crystal TiO₂, but the breakdown voltage is close to 0.5 V (versus that of a saturated calomel electrode). The short-circuit photocurrent density (J _SC) increases with a decrease of donor concentration, which was calculated according to the Gartner-Butler model. For the lowest donor concentration of a TiO₂-5%ZnO electrode sprayed under an arc current of 600 A, the short-circuit J _SC is approximately 0.4 mA/cm² higher than that of the TiO₂ electrodes under 30 mW/cm² xenon light irradiation. The J _SC increases linearly with light intensity. The original version of this paper was published as part of the DVS Proceedings: “Thermal Spray Solutions: Advances in Technology and Application,” International Thermal Spray Conference, Osaka, Japan, 10–12 May 2004, CD-Rom, DVS-Verlag GmbH, Düsseldorf, Germany.     

Thermoelectric Properties of Cu-doped Bi<Subscript>2−x</Subscript>Sb<Subscript>x</Subscript>Te<Subscript>3</Subscript> Prepared by Encapsulated Melting and Hot Pressing

P-type Bi_2?xSb_xTe₃:Cu_m (x = 1.5–1.7 and m = 0.002–0.003) solid solutions were synthesized using encapsulated melting and were consolidated using hot pressing. The effects of Sb substitution and Cu doping on the charge transport and thermoelectric properties were examined. The lattice constants decreased with increasing Sb and Cu contents. As the amount of Sb substitution and Cu doping was increased, the electrical conductivity increased, and the Seebeck coefficient decreased owing to the increase in the carrier concentration. All specimens exhibited degenerate semiconductor characteristics and positive Hall and Seebeck coefficients, indicating p-type conduction. The increased Sb substitution caused a shift in the onset temperature of the intrinsic transition and bipolar conduction to higher temperatures. The electronic thermal conductivity increased with increasing Sb and Cu contents owing to the increase in the carrier concentration, while the lattice thermal conductivity slightly decreased due to alloy scattering. A maximum figure of merit, ZT_max = 1.25, was achieved at 373 K for Bi_0.4Sb_1.6Te₃:Cu_0.003.     

Solvothermal synthesis and thermoelectric properties of skutterudite compound Fe（0.25）Ni（0.25）Co（0.5）Sb3

Nanostructured skutterudite-related compound Fe_0.25Ni_0.25Co_0.5Sb₃ was synthesized by a solvothermal method using FeCl₃, NiCl₂, CoCl₂, and SbCl₃ as the precursors and NaBH₄ as the reductant. The solvothermally synthesized powders consisted of fine granules with an average particle size of tens of nanometers. The bulk material was prepared by hot pressing the powders. Transport property measurements indicated a heavily doped semiconductor behavior with n-type conduction. The thermal conductivity is about 1.83 W·m⁻¹·K⁻¹ at room temperature and decreases to 1.57 W·m⁻¹·K⁻¹ at 673 K. The low thermal conductivity is attributed to small grain size and high porosity. A maximum dimensionless figure of merit of 0.15 is obtained at 673 K.     

Sol-gel preparation and characterization of Li1.3Al0.3Ti1.7（PO4）3 sintered with flux of LiBO2

Li_1.3Al_0.3Ti_1.7(PO₄)₃ pellets sintered with different mole fractions of LiBO₂ were prepared by sol-gel method. The structural identification, surface morphology, ionic conductivity, and activation energy of the pellets were studied by X-ray diffraction, scanning electron microscopy, and electrochemical impedance spectroscopy. The results show that all the Li_1.3Al_0.3Ti_1.7(PO₄)₃ pellets sintered with different mole fractions of LiBO₂ have similar X-ray diffraction patterns. The sintered pellet becomes denser and the boundary and corner of the particles become illegible with the increase of LiBO₂. Among the Li_1.3Al_0.3Ti_1.7(PO₃)₄ pellets sintered with different mole fractions of LiBO₂, the one sintered with 1 mol% LiBO₂ shows the highest ionic conductivity of 3.95×10⁻⁴ S.cm⁻¹ and the lowest activation energy of 0.2469 eV.     

Electrochemical properties of spinel compound LiNi_（0.5）Mn_（1.2）Ti_（0.3）O_4 as cathode materials for lithium ion batteries

The electrochemical properties of spinel compound LiNi0.5Mn1.2Ti0.3O4 were investigated in this study.The chemicals LiAc·2H2O,Mn(Ac)2·2H2O,Ni(Ac)2·4H2O,and Ti(OCH3)4 were used to synthesize LiNi0.5Mn1.2Ti0.3O4 by a simple sol-gel method.The discharge capacity of the sample reached 134 mAh/g at a current rate of 0.1C.The first and fifth cycle voltammogram almost overlapped,which showed that the prepared sample LiNi0.5Mn1.2Ti0.3O4 had excellent good cycle performance.There were two oxidation peaks at 4.21 V and 4.86 V,and two reduction peaks at 4.55 V and 3.88 V in the cycle voltammogram,respectively.By electrochemical impedance spectroscopy and its fitted result,the lithium ion diffusion coefficient was measured to be approximately 7.76 × 10?11 cm2/s.