Enhanced thermoelectric properties of Co1-x-yNix+ySb3-xSnx materials

Co_1−x−y Ni_x+y Sb_3−x Sn _x polycrystals were fabricated by vacuum melting combined with hot-press sintering. The effect of alloying on the thermoelectric properties of unfilled skutterudite Co_1−x Ni _x Sb_3−x Sn _x was investigated. A leap of electrical conductivity from the Co_0.93Ni_0.07Sb_2.93Sn_0.07 sample to the Co_0.88Ni_0.12Sb_2.88Sn_0.12 sample occurs during the measurement of electrical conductivity, indicating the adjustment of band structure by proper alloying. The results show that alloying enhances the power factor of the materials. On the basis of alloying, the thermoelectric properties of Co_0.88Ni_0.12Sb_2.88Sn_0.12 are improved by Ni-doping. The thermal conductivities of Ni-doping samples have no reduction, but their power factors have obvious enhancement. The power factor of Co_0.81Ni_0.19Sb_2.88Sn_0.12 reaches 3.0 mW·m⁻¹·K⁻² by Ni doping. The dimensionless thermoelectric figure of merit reaches 0.55 at 773 K for the unfilled Co_0.81Ni_0.19 Sb_2.88Sn_0.12.     

Refinement of the crystal structure for a new mineral──antimonselite

The crystal structure of a new mineral of the stibnite group, Sb-2Se-3, has been determined. The cell constants, obtained by least-squares calculation from direct θ -value's measurements on the diffractometer are: a =1.158 8(5), b =1.174 4(4), c =0.395 5(2) nm; orthorhombic; V =0.538 23 nm+3; Z =4. The space group is Pbnm. X-ray single crystal data, using Mo K α radiation, were measured on a RIGAKU RASA-5RP automated diffractometer and refined to a final R index of 0.048 1. Sb-2Se-3 is isostructural with Sb-2S-3 and Bi-2S-3. Each Sb(1) atom is six-coordinated by 3 Se(1), 1 Se(2) and 2 Se(3) atoms at distances 0.266 0-0.323 6 nm. Each Sb(2) atom is seven-coordinated by 2 Se(1), 2 Se(2) and 3 Se(3) atoms at distances of 0.258 1- 0.346 7 nm. The crystal structure consists of chains parallel to c or needle axis. The strongest bonds (shortest separations) are within the chains. Many important physical properties of antimonselite (optical, ferroelectric, etc.) are related to its crystal structure.     

Doping effect on thermoelectric properties of nonstoichiometric AgSbTe<Subscript>2</Subscript> compounds

Nonstoichiometric ternary thermoelectric materials Ag_0.84Sb_1.15M_0.01Te_2.16 (M=Ce, Yb, Cu) were prepared by a direct melt-quench and hot press process. The carrier concentration of all the samples increased after doping. Thermoelectric properties, namely electrical conductivity, Seebeck coefficient, and thermal conductivity, were measured from 300 to 673 K. The phase transition occurring at about 418 K representing the phase transition from β-Ag₂Te to α-Ag₂Te influenced the electrical transport properties. The electrical conductivities of Ce and Yb doped samples increased after doping from 1.9×10⁴ to 2.5×10⁴ and 2.3×10⁴ S·m⁻¹, respectively, at 673 K. Also, at room temperature, the Seebeck coefficient of the Ce doped sample relatively increased corresponding to the high carrier concentration due to the changes in the band structure. However, all the thermal conductivities increased after doping at low temperature. Because of the higher thermal conductivity, the dimensionless figure of merit ZT of these doped samples has not been improved.     

Influence of modulation period for β-Cu2+xSe/SiC nano-multilayer films on their thermoelectric properties

In this study, β-Cu_2+xSe/SiC nano-multilayer films with different modulation period were successfully deposited on SiO₂/Si substrates by sputtering alternately using Cu–Se and SiC targets. The deposited films were observed on both surface and cross-section, and the thermoelectric properties were studied. The results show that both carrier concentration and mobility at room temperature decreased with the reducing modulation period for the nano-multilayer films. The conductivity slightly decreased and Seebeck coefficient greatly increased with the reducing modulation period. As a result of competition, the power factor of the nano multilayer films increased with the reducing modulation period because the positive effect of the Seebeck coefficient exceeded the negative effect of the conductivity. In the case of β-Cu_2+xSe/SiC nano multilayer film with the smallest modulation periods (210 ?nm), the power factor reached 0.39 ?mWm^?1K^?2 and 0.59 ?mWm^?1K^?2 at room temperature and 325 ?°C, respectively. The enhanced power factor for nano multilayer films is attributed to the scattering process at the β-Cu_2+xSe/SiC layer interface, which reduces the carrier concentration and the mobility. It is concluded that the thermoelectric properties of β-Cu_2+xSe films can be effectively improved by designing nano multilayer structure.     

Dielectric,piezoelectric, and ferroelectric properties of lanthanum-modified PZTFN ceramics

Specimens of Pb_1?1.5xLa_x(Zr_0.53Ti_0.47)_1?y?zFe_yNb_zO₃(x = 0, 0.004, 0.008, 0.012, and 0.016, y = z = 0.01) (PZTFN) ceramics were synthesized by a semi-wet route. In the present study, the effect of La doping was investigated on the structural, microstructural, dielectric, piezoelectric, and ferroelectric properties of the ceramics. The results show that, the tetragonal (space group P4mm) and rhombohedral (space group R3c) phases are observed to coexist in the sample at x = 0.012. Microstructural investigations of all the samples reveal that La doping inhibits grain growth. Doping of La into PZTFN improves the dielectric, ferroelectric, and piezoelectric properties of the ceramics. The hysteresis loops of all specimens exhibit nonlinear behavior. The dielectric, piezoelectric and ferroelectric properties show a maximum response at x ≥ 0.012, which corresponds to the morphotropic phase boundary (MPB).     

Microstructure, crystalline phase and electrical properties of Li0.06(Na0.5K0.5)0.94Nb(1−2x/5)Mg x O3 lead-free piezoelectric ceramics

MgO-modified Li_0.06(Na_0.5K_0.5)_0.94NbO₃ (L₆NKN) lead-free piezoelectric ceramics were synthesized by normal sintering at a relatively low temperature of 1000°C. The crystalline phase, microstructure, and electrical properties of the ceramics were investigated with a special emphasis on the influence of MgO content. The addition of MgO effectively improves the sinterability of the L₆NKN ceramics. X-ray diffraction analysis indicates that the morphotropic phase boundary (MPB) separating orthorhombic and tetragonal phases for the ceramics lies in the range of Mg doping content (x) from 0.3at% to 0.7at%. High electrical properties of the piezoelectric constant (d ₃₃=238 pC/N), planar electromechanical coupling coefficient (k _p=41.5%), relative dielectric constant (? _r=905), and remanent polarization (P _r=38.3 μC/cm²) are obtained from the specimen with x=0.5at%, which suggests that the Li_0.06(Na_0.5K_0.5)_0.94Nb_(1?2x/5)Mg _x O₃ (x=0.5at%) ceramic is a promising lead-free piezoelectric material.     

Mechanical and thermal properties of NpO2 using LSDAt U approach

The elastic constants,bulk modulus,shear modulus,Young’s modulus,Debye temperature,isobaric heat capacity and minimum thermal conductivity are estimated for NpO2 using plane-wave pseudopotential method within the local spin density approximation plus Hubbard U(LSDAtU) theory.The computed lattice constants are in good agreement with the available experimental results and then three independent elastic constants were computed by means of the stress–strain method.From the knowledge of the elastic constants,the values of Young’s modulus,Poisson,Debye temperature and minimum thermal conductivity are obtained and they are 218 GPa,0.288,453.5 K and0.99 Wm-1K-1,respectively.The obtained mechanical and thermal properties of NpO2 are in agreement with the previous experimental and theoretical data.Our investigations which are unobtainable from previous report can provide valuable reference in the future.     

Morphological evolution and kinetic enhancement of Li2FexMn1-xSiO4/C cathodes for Li-ion battery

Li_2MnSiO_4-based cathode materials possess reasonable work potentials and high theoretical capacities,while the practical energy/power densities are constrained by their inferior kinetics of Li~+ diffusion.In this work,the Pmn2_1-structure Li_2Fe_xMn_(1-x)SiO_4/C materials were synthesized via a solvothermal method and evaluated as Liion cathode materials,with notable morphological evolutions and tunable crystallographic habits observed after solvothermal process.The Li_2Fe_(0.33)Mn_(0.67)SiO_4/C material delivers an initial reversible capacity of 250.2mAh g~(-1)at 0.1 C(～1.51 Li~+insertion/extraction,1 C=166 mA g~(-1)),excellent high-rate capability(52.2 mAh g~(-1)at 5 C),and good long-term cyclability(64.6%after 196 cycles at 2 C).The enhanced electrochemical properties are attributed to the boosted ion/electron transports induced by preferred morphological and structural characteristics of Li_2Fe_(0.33)Mn_(0.67)SiO_4/C.     

InAsSb thick epilayers applied to long wavelength photoconductors

InAs_0.052Sb_0.948 epilayers with cutoff wavelengths longer than 8 μm were successfully grown on InAs substrates using melt epitaxy (ME). Scanning electron microscopy observations show that the interface between the epilayers and substrates is flat, indicating the good quality of the epilayers, and the thickness of the epilayers is 40 μm. Photoconductors were fabricated using InAs_0.052Sb_0.948 thick epilayers grown by ME. Ge optical lenses were set on the photoconductors. At room temperature, the photoresponse wavelength range was 2–10 μm. The peak detectivity D_λp* reached 5.4 × 109 cm·Hz1/2·W?1 for the immersed detectors. The detectivity D* was 9.3 × 108 and 1.3 × 108 cm·Hz1/2·W?1 at the wavelength of 8 and 9 μm, respectively. The good performance of the uncooled InAsSb detectors was experimentally validated.     

Scalable synthesis and electrochemical performance of mesoporous graphene from calcium carbonate by magnesiothermic reaction

A novel scalable synthetic method of mesoporous graphene has been developed using the compressed mixture of Mg and excess CaCO₃ in a closed container. The generated solid oxide and unreacted CaCO₃ could act as mesopore-forming agents, and the closed container could prevent the carbon dioxide from CaCO₃ flow away. As a result, the graphenes with a large number of 2–30 ?nm mesopores and high utilization ratio of Mg achieved. The graphenes had high specific surface area and excellent electrochemical performance. In particular, the Mg utilization ratio was up to 53.3% in the preparation of graphene using 2:1 CaCO₃/Mg at 700 ?°C, which is superior to previous researches. The obtained mesoporous graphene exhibited high specific surface area of 743.7 ?m² ?g^-1, large specific capacitance of 140 ?F ?g^-1, and high capacitance retention rate of 64.3%.     

Dielectric properties, electrical modulus and current transport mechanisms of Au/ZnO/n-Si structures

Au/Zn O/n-Si(MIS)structures were fabricated by using the RF sputtering method and their complex dielectric constant(ε~*=ε’-jε’’),electric modulus(M~*=M′+j M’’)and electrical conductivity(σ=σ_(dc)+σ_(ac))values were investigated as a function of frequency(0.7 k Hz-1 MHz)and voltage(-6–(+6 V))by capacitance-voltage(C-V)and conductance-voltage(G/ω-V)measurements to get more information on the conduction mechanisms and formation of barrier height between Au and n-Si.The lnσ-Lnf plots have two different regions corresponding to low-intermediate and high frequencies.Such behavior of lnσ-lnf plots shows that the existence of two different conduction mechanisms(CMs)at low-intermediate and high frequencies.Moreover,the reverse bias saturation current(I_o),ideality factor(n),barrier height(Φ_(Bo))were determined from the forward bias I-V data and they were found as a strong function of temperature.The value of n especially at low temperature is considerably higher than unity.The values ofΦ_(B0)and standard deviation(σ_s)were found from the intercept and slope ofΦ_(Bo)-q/2k T plots as 0.551 e V and 0.075 V for the region I(80–220 K)and 1.126 e V and 0.053 V for the region II(220–400 K),respectively.The values ofΦ_(Bo)and effective Richardson constant(A~*)were found from slope and intercept of activation energy plots as 0.564 e V and 101.084 Acm~(-2)K~(-2)for the region I and 1.136 e V and41.87 Acm~(-2)K~(-2)for the region II,respectively.These results confirm that the current-voltage-temperature(I-V-T)characteristics of the fabricated Au/Zn O/n-Si SBDs can satisfactorily be explained on the basis of TE theory with double GD of the BHs.     

Effects of Gd solutes on hardness and yield strength of Mg alloys

Relative contribution of individual strengthening mechanisms to the yield strength of Mg–0–15 wt%Gd alloys were investigated.Alloys with different grain size were prepared by adding Zr and hot extrusion.Hardness and tensile/compression yield strength were tested on the alloys after solid solution treatment and extrusion.HallPetch constants were calculated with hardness and tensile/compressive data.The results showed that the hardness of Mg–Gd alloys with similar Gd content and different grain size were almost the same,which indicates that grain size had little effect on hardness.The hardness linearly increased with rising Gd content(d H_v/dc≈25 kg mm~(-2)/at%Gd).The tensile and compressive yield strengths enhanced with the increase of Gd content for all alloys in different conditions.In addition,the tensile/compressive(t/c)yield asymmetry of extruded alloys decreased with increasing Gd content.Large t/c yield asymmetry ratio(1.77)was observed for pure Mg,and with increasing Gd content this value decreased to 1.With the increasing of tensile strength,the stress intensity factor,k_y,decreased from 0.27 MPa m~(1/2)for Mg–2 wt%Gd alloy to 0.19 MPa m~(1/2) for Mg–5 wt%Gd alloy,then increased to 0.29 MPa m~(1/2) for Mg–15 wt%Gd alloy.However,k_yincreased linearly form 0.16–0.31 MPa for compression test.The influence of grain size strengthening was eliminated,and the yield strength of tension and compression both linearly increased with c~n,where c is the atom concentration of Gd,and n=1/2 or 2/3.     

Phase analysis and thermal conductivity of in situ O′-sialon/β-Si3N4 composites

Typical O??-sialon-based ceramics, with a formula of Si_2?x Al _x O_1+x N_2?x , where x was set as 0.25, were fabricated by in-situ synthesis. Si₃N₄, Al₂O₃, and SiO₂ powders were used as raw materials, and MgO and Y₂O₃ were added as sintering additives. All the samples were sintered at different temperatures under a nitrogen pressure of 0.25?C0.30 MPa, and their microstructure, phase content, and thermal conductivity were evaluated. The effects of O??-sialon and ??-Si₃N₄ on the thermal conductivity were analyzed by numerical calculation in detail. In the case of the similar porosity, the thermal conductivity of O??-sialon-based ceramics decreased with the ratio of O??-sialon/??-Si₃N₄ increasing. When the ratio was 12, the thermal conductivity of O??-sialon ceramics sintered at 1360°C was 1.197 W·m^?1·K^?1.     

Structure and effect of diamagnetism on manganese lithium phosphate glass to cathode materials application

1-x(Li₂O–2P₂O₅)-xMnO₂ glasses where x ?= ?0.2, 0.3 and 0.4 ?mol%, respectively, were synthesized by melted-quenching method. The Mn and P oxidation states and local structures around Mn and P-ions including Mn–O and P–O bonding distances and coordination numbers have been studied via X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), respectively. XANES results exhibit a coexistence of oxidation state of Mn²⁺ and Mn³⁺ with a mean value of 2.82. Moreover, Mn and P K-edge EXAFS show the Mn–O and P–O bonding distances of approximately 2.083–2.094 ?Å and 1.766–1.774 ?Å, respectively. A paramagnetism was found for all Mn–P glasses. Additionally, the coercive field (H_c) and remnant magnetization (M_r) increased with increasing Mn contents. However, the low specific capacitances are seriously obtained (<40 ?F ?g^?1) suggesting the effect of natural diamagnetism of lithium phosphate based-glass unlike the borate based-glasses which originally exhibit paramagnetism.     

Hydrogen absorption-desorption characteristic of (Ti0.85Zr0.15)1.1Cr1-xMoxMn based alloys with C14 Laves phase

The microstructure and hydrogen absorption-desorption characteristic of (Ti_0.85Zr_0.15)_1.1Cr_1-xMo_xMn (x ?= ?0.05, 0.1, 0.15, 0.2 ?at.%) alloys were investigated. The results showed that the corresponding alloys were determined as a single phase of C14-type Laves structure. With the increase of Mo content, the maximum and reversible hydrogen absorption capacity decreased, the slope factor H_f increased. Among the studied alloys, (Ti_0.85Zr_0.15)_1.1Cr_0.95Mo_0.05Mn had the best overall properties for practical application of hydrogen storage materials. The maximum and reversible hydrogen storage capacity were 1.76 ?wt% and 1.09 ?wt%, the slope factor H_f was 0.51, and its dissociation enthalpy (ΔH_d) and entropy change (ΔS_d) were 23.1 ?kJ ?mol^?1H₂, 93.8J ?K^?1mol^?1H₂ at 303K, respectively. By studying the dissociation pressures of the synthesized metal hydrides, it was found that Mo had a special effect on the dissociation pressure of Ti–Zr–Cr–Mo–Mn alloys. Among the four alloys, (Ti_0.85Zr_0.15)_1.1Cr_0.95Mo_0.05Mn alloy had the largest hydrogen absorption capacity and the fastest hydrogen desorption rate, which can meet the commercialization demand of hydrogen fuel cell hydrogen supply system.     

Highly stable N-containing polymer-based Fe/Nx/C electrocatalyst for alkaline anion exchange membrane fuel cell applications

A cost-effective electrocatalyst with high activity and stability was developed. The Fe-Nx and pyridinic-N active sites were embedded in nitrogen-doped mesoporous carbon nanomaterial by carbonization at high temperature. The electrocatalyst exhibited excellent electrochemical performance for the oxygen reduction reaction, with high onset potential and half-wave potential values (E_onset = 1.10 ?V and E_1/2 ?= ?0.944 ?V) than 20 ?wt % Pt/C catalyst (1.04 and 0.910 ?V). The mass activity of the Schiff base network (SNW) based SNW-Fe/N/C@800° electrocatalyst (0.64 ?mA ?mg^?1 @ 1 ?V) reached about half of the commercial Pt/C electrocatalyst (1.35 ?mA ?mg^?1 @ 1 ?V). The electrocatalyst followed the 4-electron transfer mechanism due to very low hydrogen peroxide yield (H₂O₂ ?< ?1.5%) was obtained. In addition, this electrocatalyst with dual active sites showed high stability during cyclic voltammetry and chronoamperometry measurements. More importantly, the electrocatalyst also demonstrated the power density of 266 ?mW ?cm^?2 in the alkaline anions exchange membrane fuel cell (AEMFC) test, indicating its prospective application for fuel cells.     

A ternary FeS_2/Fe_7S_8@nitrogen-sulfur co-doping reduced graphene oxide hybrid towards superior-performance lithium storage

Iron sulfides are promising anode materials for lithium ion batteries(LIBs) owe to their high theoretical capacity and low cost. However, unsatisfactory electronic conductivity, dissolution of polysulfides, and severe agglomeration during the cycling process limit their applications. To solve these issues, a ternary FeS_2/Fe_7S_8@nitrogensulfur co-doping reduced graphene oxide hybrid(FeS_2/Fe_7S_8@NSG) was designed and synthesized through a facile hydrolysis-sulfurization strategy, in which the FeS_2/Fe_7S_8 could be well distributed upon the NSG. The NSG was believed to buffer the volume change and augment the electronic conductivity of the electrode, and the nanodimensional FeS_2/Fe_7S_8 particles with a diameter of 50–100 nm could shorten the ion-diffusion paths during the lithiation/delithiation process. Benefiting from synergistic contributions from nano-dimensional FeS_2/Fe_7S_8 and flexible NSG, the FeS_2/Fe_7S_8@NSG hybrid displayed a high initial capacity of ～1068 m Ah g~(-1) at 200 mA g~(-1),good cycling stability(～898 mAh g~(-1) at 500 mA g~(-1) after 200 cycles) and high-rate performance. Further kinetic analysis corroborated that the introduction of NSG boosted the capacitive behavior. Above results indicate the potential applications of FeS_2/Fe_7S_8@NSG hybrid in LIBs with low-cost and high energy density.     

PbxNayYzF2x+y+3z+3m∶Erm3+上转换发光粉的低温燃烧合成及表征

采用低温燃烧合成（LCS）法一步合成了Pb_xNa_yY_zF_2x+y+3z+3m:Er_m3+氟化物体系1 550 nm响应的红外上转换发光材料. 通过正交实验研究了4种阳离子影响发光性能的主次关系及最佳配比,研究了燃料用量对晶相形成及上转换发光性能的影响. 采用X射线粉末衍射仪、透射电镜、荧光分光光度计（耦合1 550 nm激光器）等手段对样品的物相、形貌及发光性能进行了测试与表征. 结果表明:阳离子含量对红光发射强度影响的主次关系为Y3+,Pb2+,Na+,Er3+,最佳配比为Pb_0.004Na_0.003 Y_0.003 F_0.032:Er3+_0.004. 燃料取2.5倍理论用量时样品的结晶度和发光强度最高.      

Metal ion-binding properties of wild-type and mutant D37K of ciliate Euplotes octocarinatus centrin

Ciliate Euplotes octocarinatus centrin (EoCen) is an EF-hand calcium-binding protein closely related to the prototypical calcium sensor protein calmodulin. The first amino acid of the Ca²⁺-binding loops found in the EF-hand calcium-binding proteins is a highly conserved aspartic acid residue. The D37K mutant was produced to elucidate the metal binding role of the first aspartic acid of the EF-loop I of EoCen. Aromatic-sensitized Tb³⁺ fluorescence results indicated that the metal binding ability of loop I was lost due to the D37K mutation. Based on fluorescence titration curves of Lu₂-D37K, the conditional binding constants of the EoCen loop II were quantitatively found to be K _II = (1.61 ± 0.04) × 10⁵ L mol^?1 and K _II = (3.52 ± 0.08) × 10² L mol^?1 with Tb³⁺ and Ca²⁺, respectively. Using 2-p-toluidinylnaphthalene-6-sulfonate as a hydrophobic probe, exposure of the hydrophobic surface upon metal binding was found to be significantly reduced for the metal ion-saturated EoCen D37K mutant.     

Effects of Ce, Y, and Sm doping on the thermoelectric properties of Bi2Te3 alloy

Nanopowders of elements doped Bi2Te3thermoelectric alloy R0.2Bi1.8Te3(R Ce,Y and Sm)were synthesized by the hydrothermal method.The nanopowders were hot-pressed into pellets and their thermoelectric properties were investigated.The results show that Ce,Y,and Sm doping has signifcant effects on the morphologies of the synthesized nanopowders and thermoelectric properties.Among the doping elements,Ce doping is a superiority dopant.Although the electrical conductivity and Seebeck coeffcient are not improved much by Ce doping,the thermal conductivity is supressed greatly.As a result the fgure of merit(ZT) of Ce0.2Bi1.8Te3is improved and reaches 1.29 at 398 K,which is higher than the Bi2Te3ingots made by the traditional zone-melting method