Sn3InSb4合金嵌Li性能的第一性原理研究

采用第一性原理超软赝势平面波方法计算了Sn₃InSb₄的嵌Li性能,得到各种嵌Li相的嵌Li形成能、理论质量比容量、体积膨胀率、能带结构、态密度和差分电荷密度等.从能量角度分析,Li在嵌入时,优先占据晶胞的四面体间隙位置,然后逐步挤出处于节点位置的Sn原子和In原子.在嵌Li过程中,材料表现出较大的体积膨胀率(11.74%-43.40%),这是导致Sn₃InSb₄作为Li离子电极材料循环性能差的重要原因.态密度计算表明,体系的导电性能首先随嵌Li量的增加而增加,当所有的间隙位置被Li填满,发生Sn的替换反应时,富Li态合金相的导电性反而下降.     

Nanostructured Ni3Sn2 thin film as anodes for thin film rechargeable lithium batteries

Thin film Ni₃Sn₂ anodes were deposited on a Cu substrate by e-beam evaporator at room temperature. The deposited films were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). They were tested as anodes for thin film rechargeable lithium batteries. These film electrodes exhibited an excellent cycle performance over 500 cycles. Ni₃Sn₂ films remained without undergoing any crystallographic phase change during cycling.     

Mn3Zn0.8Ni0.2N的高压同步辐射研究

 利用金刚石对顶压砧,对钙钛矿型金属锰化物Mn₃Zn_0.8Ni_0.2N进行了原位高压同步辐射角散X射线衍射研究。研究表明,在0~29.9 GPa的压力区间内,样品没有发生结构相变,因而在该压力下样品的物性变化并非由结构相变所导致。卸压以后,样品的特征峰都回到了初始位置。通过Birch-Murnaghan方程,拟合得到了样品的体弹模量为86.5 GPa。     

The influence of Al substitution on the phase transitions and magnetocaloric effect in Ni43Mn46Sn11−xAlx alloys

The effects of Al substitution on the phase transitions and magnetocaloric effect of Ni₄₃Mn₄₆Sn_11−xAl_x (x=0-2) ferromagnetic shape memory alloys were investigated by X-ray diffraction and magnetization measurements. With the increase of Al content, the cell volume decreases due to the smaller radius of Al, and the martensitic transformation temperature increases rapidly, while the Curie temperature of austenitic phase shows a small increase. A large positive and a negative magnetic entropy change were observed near the first-order martensitic transition and the second-order magnetic transition, respectively. The magnetic entropy changes, hysteresis behavior, and refrigerant capacity near the two transitions are compared.     

NbTi0.5Ni0.5O4 as anode compound material for SOFCs

NbTi_0.5Ni_0.5O₄ (NTNO) has been prepared using solid state synthesis and investigated as a potential anode material. The oxide form of NTNO has single phase rutile-type structure with tetragonal (P42/mnm) space group. The reduced form is a composite of nano-scaled particles of metallic Ni and Nb_1.33Ti_0.67O₄ phase. Reduced NTNO showed high electronic conductivity up to 280 S.cm^− 1 at 900 °C in reducing atmosphere, but suffers from low CTE equal to 3.78 10^− 6 K^− 1. Studies of NTNO as anode material were carried out in a three electrode - electrochemical half cell configuration under pure humidified H₂ at 900 °C using a 2 mm thick zirconia electrolyte and without any additional current collector material. The results show a reasonable series resistance (R_s) equal to 2.7 Ωcm² (about 50% higher than for metallic gold layers) indicating a good current collection performance for a 10 μm layer of material. The polarization resistance (R_p) was equal to 33 Ωcm² and is attributed to a poor density of three phase boundaries (TPB) and shortage of oxide ion conduction in the anode layer. The results show the potential of NTNO as an anode material, especially after optimization of the microstructure towards the increase of TPB length.     

Microstructure characterization and magnetic behavior of NiAlxFe2−xO4 and Ni1−yMnyAl0.2Fe1.8O4 ferrites

NiAl_xFe_2−xO₄ and Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites were prepared by the conventional ceramic method and were characterized by X-ray diffraction, scanning electron microscopy, and magnetic measurements. The single spinel phase was confirmed for all prepared samples. A proper explanation of data is possible if the Al³⁺ ions are assumed to replace Fe³⁺ ions in the A and B sites simultaneously for NiAl_xFe_2−xO₄ ferrites, and if the Mn²⁺ ions are assumed to replace Ni²⁺ ions in the B sites for Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites. Microstructural factors play an important role in the magnetic behavior of Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites with large Mn²⁺ content.     

Electrochemical studies on mixtures of LiNi0.8Co0.17Al0.03O2 and LiCoO2 cathode materials for lithium ion batteries

Detailed electrochemical investigations have been carried out on LiNi_0.8Co_0.17Al_0.03O₂ as cathode materials for lithium ion batteries in the potential range of 2.8-4.3 V. This sample showed an initial discharge capacity of 186 mAh/g which corresponds to 67% of its theoretical capacity. The effect of addition of LiCoO₂ to LiNi_0.8Co_0.17Al_0.03O₂ in the ratio 10:90, 30:70, 50:50 has been studied. The results showed that the addition of LiCoO₂ has improved the working voltage of the cell. In addition, the percentage retention (95%) of the cell is significantly increased in the composition ratio 50:50.     

Giant room-temperature magnetoresistance in La0.8Tb0.2MnO3 under the low magnetic fields

Polycrystalline perovskite La_0.8Tb_0.2MnO₃ (LTMO) with an orthorhombic phase was synthesized by conventional solid-state reaction. The magnetic and electric properties of La_0.8Tb_0.2MnO₃ were examined. The striking finding is that the material exhibits giant magnetoresistance at room temperature as high as −31.8% and −35.7% under the low magnetic fields of 100 and 1000 Oe, respectively. This result suggests that La_0.8Tb_0.2MnO₃ has a promising potential in future device developments.     

Determination of the magnetocaloric effect associated with martensitic transition in Ni46Cu4Mn38Sn12 and Ni50CoMn34In15 Heusler alloys

This paper presents a study of the inverse magnetocaloric effect (MCE) corresponding to martensitic transition using various experimental approaches for Ni46Cu4Mn38Sn12 and Ni50CoMn34In15 Heusler alloy. Through heat capacity measurements,it is found that the "giant inverse MCE" upon martensitic transition evaluated by the Maxwell relation in these alloys are unphysical results. This is due to the coexistence of both martensitic and austenitic phases,as well as thermal hysteresis during martensitic transition. However,careful study indicates that the spurious results during martensitic transition can be removed using a Clausius-Clapeyron equation based on magnetization measurements.     

Electrical resistivity of the pseudo-binary compound Ce(Fe0.8Al0.2)2

Electrical resistivity measurements on the alloy Ce(Fe_0.8Al_0.2)₂ as a function of temperature in the range of 1.5 to 300 K shows that the long range magnetic order of the CeFe₂ is destroyed and that the spin glass phase appears with a negative coefficient of T^3/2. The high residual resistivity is also discussed.     

Sn Mössbauer spectroscopy of Gd0.8L0.2Mn6Sn6 and Tb0.8L0.2Mn6Sn6 compounds (L=Sc,Y, Lu)

The HfFe₆Ge₆-type compounds Gd_0.8L_0.2Mn₆Sn₆ and Tb_0.8L_0.2Mn₆Sn₆ (L = Sc, Y, Lu) have been studied by ¹¹⁹Sn Mössbauer spectroscopy. The values of the apparent quadrupolar splitting clearly evidence the easy plane magnetization of the gadolinium compounds and the easy axis one in the terbium compounds. The three tin sites behave differently with the nature and size of the substituting L element. For a given series, the hyperfine field of the Sn_2d site is almost unchanged whatever the size of the L element. The hyperfine field of the Sn_2e site strongly varies with the L size in relation with atomic displacements. The hyperfine field of the Sn_2c site exhibits a more complicated behavior. The field difference in the easy plane and easy axis compounds confirms the angle-dependent anisotropic contribution of the Mn moment to the hyperfine field. The analysis of the results also suggests the play of angle-dependent contributions arising from the rare earth moment.     

Preparation and magnetic properties of BaFe12O19/Ni0.8Zn0.2Fe2O4 nanocomposite ferrite

Nanocomposite of hard (BaFe₁₂O₁₉)/soft ferrite (Ni_0.8Zn_0.2Fe₂O₄) have been prepared by the sol–gel process. The nanocomposite ferrite are formed when the calcining temperature is above 800 °C. It is found that the magnetic properties strongly depend on the presintering treatment and calcining temperature. The “bee waist” type hysteresis loops for samples disappear when the presintering temperature is 400 °C and the calcination temperature reaches 1100 °C owing to the exchange-coupling interaction. The remanence of BaFe₁₂O₁₉/Ni_0.8Zn_0.2Fe₂O₄ nanocomposite ferrite with the mass ratio of 5:1 is higher than a single phase ferrite. The specific saturation magnetization, remanence magnetization and coercivity are 63 emu/g, 36 emu/g and 2750 G, respectively. The exchange-coupling interaction in the BaFe₁₂O₁₉/Ni_0.8Zn_0.2Fe₂O₄ nanocomposite ferrite is discussed.     

Spinel lithium titanate (Li4Ti5O12) as novel anode material for room-temperature sodium-ion battery

This is the first time that a novel anode material, spinel Li₄Ti₅O₁₂ which is well known as a “zero-strain” anode material for lithium storage, has been introduced for sodium-ion battery. The Li₄Ti₅O₁₂ shows an average Na storage voltage of about 1.0 V and a reversible capacity of about 145 mAh/g, thereby making it a promising anode for sodium-ion battery. E_x-situ X-ray diffraction (XRD) is used to investigate the structure change in the Na insertion/deinsertion process. Based on this, a possible Na storage mechanism is proposed.     

Maxwell-Wagner characterization of dielectric relaxation in Ni0.8Zn0.2Fe2O4/Sr0.5Ba0.5Nb2O6 composite

Dense composites were prepared through incorporating the dispersed Ni_0.8Zn_0.2Fe₂O₄ ferromagnetic particles into Sr_0.5Ba_0.5Nb₂O₆ ferroelectric matrix. Extrinsic dielectric relaxation and associated high permittivities of the materials are reported in the composites. We used an ideal equivalent circuit to explain electrical responses in impedance formalism. A Debye-like relaxation in the permittivity formalism was also found. Interestingly, real permittivity (ε′) of the sample containing 30% Ni_0.8Zn_0.2Fe₂O₄ shows obvious independence of the temperature at 100 kHz. Dielectric relaxation and high-ε′ properties of the composites are explained in terms of the Maxwell-Wagner (MW) polarization model.     

微观相场法模拟Ni75Al5.3V19.7 中L12和D022结构反位缺陷的演化

运用微观相场法研究Ni₇₅Al_5.3V_19.7合金沉淀过程中L1₂结构和D0₂₂结构反位缺陷发现：在沉淀初期,L1₂结构反位缺陷Al_Ni,V_Ni,Ni_Al,D0₂₂结构反位缺陷V_Ni,Al_Ni关键词： 微观相场 反位缺陷 L1₂结构')" href="#">L1₂结构 D0₂₂结构')" href="#">D0₂₂结构     

Synthesis,structural and electrical properties of Ti modified Bi2Sn2O7 pyrochlore

Polycrystalline ceramic samples of Bi₂Sn_2−xTi_xO₇ (x=0.00, 0.2, 0.4, 0.6 and 0.8) have been synthesized by standard high temperature solid state reaction method. The effect of homovalent cation (titanium) substitution on the Sn-site on the structural and electrical properties of the pure Bi₂Sn₂O₇ ceramic have been studied by X-ray diffraction followed by SEM, dielectric and dc conductivity studies. The structural analysis indicates that the increase of titanium contents do not lead to any secondary phase. The frequency and temperature dependent dielectric studies have been carried out. It is found that the Ti doping reduces the material particle size. The size of the particles are strongly influenced by the addition of titanium to the system. The substitution of Ti for Sn ions affected the degree of disorder and modified the dielectric properties leading to more resistive ceramic compounds. The activation energies of all the compounds were calculated using the relation σ=σ₀exp(−Ea/kT).     

Zr65Cu17.5Ni10Al7.5合金定向凝固组织特征及其与重力场取向的关系

研究了Zr₆₅Cu_17.5Ni₁₀Al_7.5合金定向凝固过程中组织形态的演变特征，探索了不同的凝固方向与重力场方向间的相互取向关系对凝固组织形态的影响.存在着一个临界抽拉速度V_fc,当抽拉速度大于该临界值时组织方向性变差.该合金本身的物理性质决定了它具有一个较小的临界值(V_fc=5mm/min).不同的凝固方向与重力场的相对取向关系改变了液-固界面前沿的浮力对流状态.当凝固方 关键词：     

LiPON as a protective layer on graphite anode to extend the storage life of Li-ion battery at elevated temperature

A thin-film lithium phosphorous oxynitride (LiPON) layer on the top of a graphite anode is synthesized via radio frequency magnetron sputtering, whereas the thickness of the film is about 0.3 ~ 1.3 μm. The field emission scanning electron microscopy on the samples confirms the even-coated layer on the anode, while the thickness of layer is reconfirmed by weighing the area density of sputtered anode. The storage experiment at elevated temperature of LiNi_0.8Co_0.15Al_0.05O₂/graphite cells with and without a LiPON layer on anode reveals that the LiPON layer on the anode would restrain the capacity loss when compared with bare anode. Moreover, it is found that a thicker LiPON layer on anode would provide better capacity retention during storage aging. Meanwhile, the electrochemical impedance spectroscopy is recorded during aging and its equivalent circuit simulation is proposed. Also, the anode surface morphology with and without a LiPON layer is observed before and after aging. Based on these investigations and analysis, we conclude that the LiPON layer on the top of the anode would act as a protective layer and improve the capacity retention during storage aging at elevated temperature.     

Enhancement of magnetocaloric effects in La0.8R0.2(Fe0.919Co0.081)11.7 Al1.3 (R=Pr, Nd) compounds

The magnetic properties and magnetocaloric effects (MCEs) in La_0.8R_0.2(Fe_0.919Co_0.081)_11.7Al_1.3 (R=Pr, Nd) compounds have been investigated. When Pr and Nd substitute for La, the Curie temperature of compounds decreases. The values of the MCEs are enhanced significantly by a partial substitution of Nd for La. Under the field change of 2 and 5 T, the maximum magnetic entropy changes for La_0.8Nd_0.2(Fe_0.919Co_0.081)_11.7Al_1.3 compound are −4.56 and −9.46 J/Kg K, respectively. It can be exploited for room temperature magnetic refrigeration material.     

Structural and electrochemical properties of LiNi0.4Co0.4−xAl0.2+xO2 cathode materials for lithium-ion batteries

Three Al doped lithium nickel cobalt oxide (LiNi_0.4Co_0.4−xAl_0.2+xO₂) cathode materials for lithium ion batteries were synthesized by solid state reaction method at a temperature of 800 °C for 18 hours. The samples were crystalline as revealed by powder X-Ray diffraction (XRD). The ratios of the elements were determined by Energy Dispersive Analysis of X-rays (EDAX). The electrochemical properties obtained by charge/discharge cycling showed that the average discharge capacity for LiNi_0.4Co_0.4Al_0.2O₂ was 117 mAh/g. A good capacity retention was also shown by the material upon cycling. Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6 – 8, 2005.