Structural and ion transport properties of [(AgI)x(AgBr)0.4−x](LiPO3)0.6 and (AgBr)x(LiPO3)(1−x) solid electrolytes

The (AgBr)_x(LiPO₃)_(1−x) (x=0.4 and 0.5) and [(AgI)_x(AgBr)_0.4−x](LiPO₃)_0.6 (x=0.1, 0.2, and 0.3) superionic electrolytes have been prepared by conventional melt quenching using a twin roller. These electrolytes are characterized by X-ray diffraction, SEM, and energy dispersive X-ray analysis (EDAX) for structural investigation. Electrical characterizations have been carried out by the AC impedance analysis. The conductivity of LiPO₃ glassy system at room temperature is improved by doping with the silver bromide (AgBr)_x(LiPO₃)_(1−x) and the mixture of silver iodide, silver bromide (AgI-AgBr-LiPO₃ system) up to 10⁻⁵ and 10⁻³ Ω⁻¹ cm⁻¹, respectively (improvements by four or five orders of magnitude). The frequency response of ionic conductivity has been analyzed by universal dynamic response model (Jonscher's law) and AC conductivity data are fitted using the Jonscher's power law. The conductivity values obtained by the power law and impedance plots are comparable. The frequency exponent (n) has a value between 0 and 1. The AgI-AgBr-LiPO₃ system shows the mixed alkali effect. Summerfield scaling master curve is temperature dependent, which may be due to the contribution of the both lithium and silver ions to ionic conduction.     

复合掺杂改性LiMn_(2-x)Cr_xO_(4-3x)F_(3x)正极材料的制备及性能

以CrF3为掺杂原料,采用高温固相法合成阴阳离子共掺杂LiMn2–xCrxO4–3xF3x锂离子电池正极材料。用X射线衍射、扫描电镜、充放电实验、循环伏安及交流阻抗等表征材料的结构、形貌和电化学性能,分析阴阳离子复合掺杂对材料结构和性能的影响。结果表明:掺杂材料LiMn2–xCrxO4–3xF3x具有完整的尖晶石结构。阴阳离子复合掺杂能改善尖晶石LiMn2O4的循环性能,当摩尔掺量x=0.10,电压为3.0～4.35V、充放电倍率为0.1C时,首次放电容量为120.1mA·h/g,室温、高温循环20次容量保持率分别为97.5%和94.1%。循环伏安实验发现:复合掺杂改性材料具有两对更完整、对称性更好的氧化还原峰。     

A comparative raman study of the local structure in (Ge2S3) x (As2S3)1-x and (GeS2) x (As2S3)1−x glasses

The Raman spectra of glasses in the ternary (Ge₂S₃) _x (As₂S₃)_1−x and (GeS₂) _x (As₂S₃)_1−x systems are reported. It is shown that the degree of disorder in the (Ge₂S₃) _x (As₂S₃)_1−x glasses increases with an increase in the Ge content. The differences in the spectra of glasses with the same molar content of As₂S₃ are discussed in terms of the changes occurring in the local structure due to deviations from the stoichiometry. The observed changes in the intensity of the boson peak indicate changes in the medium-range order structure of the glasses under study.     

Li_(1 x)Ti_(2-x)Ga_xP_3O_(12)和Li_(1 2x)Ti_(2-x)Mg_xP_3O_(12)系统的相关系和电导

研究了Li_(1 x)Ti_(2-x)Ga_xP_3O_(12)和Li_(1 2x)Ti_(2-x)Mg_xP_3O_(12)系统的组成、结构和电性的关系。在这两个系统中,Ga~(3 )和Mg~(2 )都能在一定的组成范围内取代LiTi_2P_3O_(12)中的Ti~(4 )形成固溶体,并使电导率提高。电导率极大值分别出现在x=0.6和x=0.3处,其在300℃左右的值为8.4×10~(-3)和5.3×10~(-3)s/cm。 比较了Ga~(3 )、Mg~(2 )和In~(3 )三种离子取代Ti~(4 )对电性的影响,并从结晶化学角度讨论了它们的差异。     

Low temperature Mössbauer spectroscopic study of CaO(Fe2O3)1−x(Al2O3)x system

Low temperature ⁵⁷Fe Mössbauer spectroscopic studies on CaO(Fe₂O₃)_1−x(Al₂O₃)_x, written as CF_1−xA_x, have been carried out. In view of the earlier findings based on room temperature data, the spectra have been analysed by assuming three Fe sites: two belonging to CF phase and the third site for the Fe atoms distributed in the CA phase. The Fe sites pertaining to the CF phase experience hyperfine field of about 49T and 47T, respectively, at 20K; whereas the third site is paramagnetic at this temperature.     

Electrical,structural and thermal properties of nanoceramic (Bi2O3)1−x−y(Ho2O3)x(Tm2O3)y ternary system

Ho₂O₃ and Tm₂O₃ doped Bi₂O₃ composite electrolyte type materials for solid oxide fuel cells (SOFCs) operating at intermediate-temperature were investigated. The bismuth-based ceramic powders were produced by using conventional solid-state synthesis techniques. The products were characterized by means of scanning electron microscopy (SEM), X-ray powder diffraction (XRD), differential thermal analysis/thermal gravimetry (DTA/TG), and the four-point probe technique (4PPT). XRD and DTA/TG measurements indicate that all of the samples have the stable fluorite type face centered cubic (fcc) δ-phase. 4PPT measurements were performed in the temperature range 150–1000 °C in air and these measurements showed that the electrical conductivity of the samples decrease with increasing amount of Tm₂O₃. This increase in the electrical conductivity of the samples could be attributed to the increase in the numbers of highly polarizable cations and oxide ion vacancies. The highest conductivity value was found as 5.31×10^?1 Ω cm^?1 for the (Bi₂O₃)_1?x?y(Ho₂O₃)_x(Tm₂O₃)_y ternary system (for x=20 and y=5 mol%) at 1000 °C. The activation energies of the samples were calculated from log σ graphics versus 1000/T. These calculated results showed that the translation motion of the charge carriers, oxygen vacancies, and space charge polarizations are responsible for the change in activation energy as a function of temperature.     

Synthesis and lithium ionic conductivity of Li3−2x(In1−xZrx)2(PO4)3 (0≦x≦0·20)

Lithium ion conductors, Li_3−2x(In_1−xZr_x)₂(PO₄)₃ (0≦x≦0·20), were synthesized by a solid state reaction. A superionic conductive phase of Li₃In₂(PO₄)₃ was stabilized down to room temperature, assisted by the substitution of Zr⁴⁺ for In³⁺ sites of Li₃In₂(PO₄)₃. TG-DTA analysis indicated no phase transition in the samples with x superior to 0·05. The substituted samples showed much higher ionic conductivity by a couple of magnitude than that of Li₃In₂(PO₄)₃. In particular, the highest conductivity at room temperature was 1·42×10⁻⁵ Scm⁻¹ for Li_2·8(In_0·9Zr_0·1)₂(PO₄)₃. Thin films with the composition of Li_2·8(In_0·9Zr_0·1)₂(PO₄)₃ was prepared by a sol–gel method. A coating solution was made from lithium isopropoxide, indium isopropoxide, zirconium isopropoxide and diphosphorus pentaoxide. Well crystallized films were obtained on silicon dioxide and quartz glass substrates by dropping the coating solution, followed by firing over 873 K. In the temperatures above 473 K the lithium ionic conductivity of the film was slightly higher than that of sintered samples prepared by the solid state reaction at 1373 K.     

Na_3Zr_(2-x)Mg_xSi_(2-2x)P_(1+2x)O_(12)系统的相关系和电性能

研究了Na_3Zr_(2-x)Mg_xSi_(2-2x)P_(1+2x)O_(12)系统的组成、结构和电性能。结果表明:Mg~(2+)能在一定的组成范围内取代Na_3Zr_2Si_2PO_(12)中的Zr~(4+)形成固溶体,单相固溶体区域延伸至x=0.5;当x=0.4时固溶体的结构由单斜转变为三方。固溶体的电导率随x的增加而降低。本文还从结晶化学的角度讨论了Na_3Zr_(2-x)Mg_xSi_(2-2x)P_(1+2x)O_(12)系统的组成、结构和电性能的关系。     

Microstructure and properties of (1 − x)La0.9Ca0.1CrO3/x ZrO2 (x = 0–30 wt-%) composites

The microstructure and properties of Ca doped lanthanum chromate [La_0.9Ca_0.1CrO₃ (LCCO)] and zirconia (ZrO₂) composites [abbreviated as (1???x)LCCO/xZrO₂, x?=?0–30?wt-%] prepared by solid state reaction method are investigated in this paper whose potential application in heat resistant ceramics are also discussed. The growth and fusion of the LCCO grains are hindered by the ZrO₂ grains, which make the matrix grains refined. In the stable system, it is discovered that the density of the composites decreases, the porosity increases and the decrease amplitude of the bend strength after thermal shock at 600°C reduces with the increasing ZrO₂ content, which results in diminishing the bend strength gradually and enhancing the thermal shock resistance. When x?=?10–15?wt-%, the samples show the best thermal shock resistance realising a maximum thermal cycle times of 8. The material with x?=?20?wt-% exhibits excellent slag resistance.     

钙钛矿陶瓷La_(1-x)Ca_xMnO_3(x=0.10,0.15,0.20)的光电子能谱

对溶胶凝胶法制备的钙掺杂LaMnO3多晶陶瓷材料La1--xCaxMnO3(x=0.10,0.15,0.20)进行了X射线衍射和各个元素的光电子能谱研究,其X射线衍射实验表明:该系列样品表现出很好的单相性,其空间结构为正交型Pbnm。Mn 2p,La4d,O 1s能级的光电子能谱结果表明:当掺杂浓度较低时,Ca离子在La位的掺杂不会引起La和O元素电子组态的变化,只引起Mn离子的化学价态变化。利用组态相互作用团簇模型计算了Mn 2p光电子能谱,得到晶体场分裂能10 Dq=1.0eV,电荷转移能Δ=5eV,d轨道之间的库伦排斥能Udd=4eV,pd轨道之间的库伦排斥能Upd=4.4eV,过渡金属离子d轨道和近邻O离子之间的轨道杂化能T(eg)=3.8eV。     

Surface Exchange of Oxygen in La1−x Sr x FeO3−δ (x = 0, 0.1)

The electronic charge carrier concentration in La_1?x Sr _x FeO_3?δ was shown to depend on the partial pressure of O₂ (pO ₂). Chemical diffusion coefficient and surface exchange coefficient, k _chem, were determined by conductivity relaxation in O₂/N₂ and CO/CO₂ mixtures. k _chem was proportional to pO ₂ ^1.06 in O₂/N₂, while in CO/CO₂ k _chem was controlled by a reaction mechanism involving both CO and CO₂.     

Magnetic properties of ferrites-cobaltites Bi1 − x La x Fe1 − x Co x O3 (1.0 ≥ x ≥ 0.7) with a perovskite structure

The molar magnetic susceptibility (χ_mol) of Bi_{1 ? x} La _x Fe_{1 ? x} Co _x O₃ solid solutions (x = 1.0, 0.9, 0.8, or 0.7) with a crystal structure of rhombohedrally distorted perovskite (R $\bar 3$ c) has been investigated in the temperature range of 5–300 K in a 0.86 T magnetic field. In the temperature range where χ_mol depends on temperature T according to the Curie-Weiss law, the resulting effective magnetic moments of Fe³⁺ and Co³⁺ ions ( $\mu _{eff,Fe^{3 + } ,Co^{3 + } ,} \mu _{eff,Fe^{3 + } } $ and $\mu _{eff,Co^{3 + } } $ ) have been determined for the solid solutions under study. Fe³⁺ ions in the solid solutions have been found to be in the mixed intermediate spin (IS) and high spin (HS) states ( $\mu _{eff,Fe^{3 + } } $ is 4.26μ_B and 4.68μ_B for the temperature range of 5–100 and 150–300 K, respectively). It is shown that 8% Co³⁺ ions in LaCoO₃ at 5–19 K are in the paramagnetic IS state and they determine to a great extent the magnetic susceptibility. It is established that only 9% and 18% Co³⁺ ions in Bi_{1 ? x} La _x Fe_{1 ? x} Co _x O₃ solid solutions (x = 0.9 or 0.8) are in the paramagnetic IS state in the temperature ranges of 5–30 and 5–110 K, respectively, while the other ions are diamagnetic.     

Li_2O掺杂Li_(3x)La_(2/3-x)TiO_3固体电解质的制备及性能

用高温固相法合成了一系列不同组成的固体电解质Li3xLa2/3-xTiO3(LLTO,x=0.06,0.10,0.12,0.16,摩尔分数),研究了不同Li2O掺杂量对LLTO显微结构和电导率的影响。对样品进行X射线衍射和扫描电子显微镜分析,用交流阻抗技术测试其电导率。结果表明:LLTO为超结构的立方晶体,在LLTO(x=0.12)陶瓷中有Li0.485La0.505TiO3相产生;1150℃烧结的样品晶粒分布较均匀且大部分为球形,1250℃烧结的样品致密度较高,晶粒的形状均匀,为片状,x=0.06时,LLTO的电导率最大,其室温电导率为1.1×10-6S/cm。     

水热法制备Ti_(3)C_(2)T_(x)-WO_(3)复合材料及其对乙醛气体的传感性能EI北大核心CSCD

工业生产生活中产生的乙醛气体需要实时高效监测,利用水热法制备了WO_(3)纳米片和一系列Ti_(3)C_(2)T_(x)-WO_(3)复合材料。采用X射线衍射法、扫描电子显微镜、Fourier红外光谱、X射线能谱等对制备出的Ti_(3)C_(2)T_(x)-WO_(3)复合材料进行了结构和形貌表征。对Ti_(3)C_(2)T_(x)-WO_(3)复合材料进行了气敏性能研究,并且探究了碳化钛加入量对Ti_(3)C_(2)T_(x)-WO_(3)复合材料气敏性能的影响。结果表明:Ti_(3)C_(2)T_(x)的加入能够有效提高WO_(3)纳米片的气敏性能。当Ti_(3)C_(2)T_(x)的加入量在7%(质量分数)时,Ti_(3)C_(2)T_(x)-WO_(3)复合材料的最佳工作温度优化为80℃。7%Ti_(3)C_(2)T_(x)-WO_(3)材料在80℃时对100μL/L的乙醛气体的灵敏度达到了32.9,最低检测限为0.1μL/L。     

黄长石Pr_(1+x)Sr_(1-x)Ga_3O_(7+0.5x)氧离子导体的制备及电性能研究

本文通过高温固相法成功合成了黄长石型Pr_(1+x)Sr_(1-x)Ga_3O_(7+0.5x) (x=0-0.4)氧离子导体材料,并对该固溶体材料进行了交流阻抗测试。结合静态晶格模拟计算数据,确定了材料的间隙氧缺陷生成能,从能量角度成功解释了含间隙氧缺陷Pr_(1+x)Sr_(1-x)Ga_3O_(7+0.5x) (x=0-0.4)氧离子导体稳定存在的可能性。材料在固态氧化物燃料电池、氧传感器等领域具有潜在应用。     

La_(0.8–x)Ba_xSr_(0.2)Co_(0.8)Fe_(0.2)O_(3–δ)阴极材料的结构与性能

采用溶胶–凝胶法制备了La0.8–xBaxSr0.2Co0.8Fe0.2O3–δ(LBSCF)阴极粉体。对LBSCF的晶体结构、材料表面的化学状态、烧结体的断面微结构及电导率进行了表征。用交流阻抗谱法在550~700℃范围测试了LBSCF-30%SDC(Sm0.2Ce0.8O1.9)复合阴极的电化学性能。结果表明:LBSCF粉体主晶相为六方晶系钙钛矿结构,存在少量的第二相。XPS结果显示,Ba2+掺杂不影响A位离子(La3+、Ba2+、Sr2+)的价态,但对B位离子的价态有不同的影响:x=0.10的样品中,钴离子以Co3+和Co4+混合价态存在,其余样品中以低氧化态(Co3+和Co2+混合价)或Co3+价存在;铁离子以高氧化态(Fe3+和Fe4+)存在。在500~700℃空气气氛中,LBSCF的电导率均超过700 S/cm,在同一温度下,电导率随着Ba2+掺杂量的增加而增大。x=0.20的样品在500℃时,电导率最大可达1.59×103 S/cm。随着Ba2+含量增加,极化电阻减小,x=0.20时,复合阴极LBSCF-30%SDC的极化电阻最小,700℃时的极化电阻为0.20?·cm2。     

单基质白光荧光粉(Ca_(0.45)Sr_(0.5)Eu_(0.05))_7(SiO_3)_6Cl_(2-2x)F_(2x)的制备及发光性能研究

采用自助熔剂法,制备出了F-掺杂的不刺眼(Ca_(0.45)Sr_(0.5)Eu_(0.05))_7(SiO_3)_6Cl_(2-2x)F_(2x)(0.5≤x≤0.9)LED用单基质白光荧光粉;利用XRD、SEM、荧光光谱等测试手段对该类荧光粉的结构、形貌及发光性能进行表征。研究表明:通过自助熔剂法合成得到了高结晶性的单基质白光荧光粉;在紫外光激发下有两个发射峰,峰位分别位于466nm和578nm左右,发光范围涵盖整个可见光区;分析认为两个发射带归结为处于两个不同发光中心上的Eu~(2+)的5d-4f发射;当掺杂量x为0.5、0.7、0.9时,在338nm激发下荧光粉均发白光。     

Li_(1+x)Ge_(2-x)Cr_xP_3O(12)系统的相关系与电导

研究了Li_(1+x)Ge_(2-x)Cr_xP_3O_(12)系统的相组成与电导的关系。用Cr~(3+)置换LiGe_2P_3O_(12)中的Ge~(4+)在00.5时出现未知相。用少量Cr~(3+)取代Ge~(4+)后电导率即骤增,在固溶体范围内电导率随x值的增大而升高,在0.2≤x≤0.6区间都有较高的电导率。Lj_(1.3)Ge_(1.7)Cr_(0.3)P_3C在35℃、300℃、450℃时的电导串分别为2.9×10~(-5)、1.1×10~(-2)、4.6×10~(-2)(S/cm),电导活化能为0.37eV,电子迁移数在10~(-5)数量级。     

Influence of vanadium substitution on sintering behaviour of Pb3(VO4)2(1−x)(PO4)2x ceramics

Intermediate-stage sintering has been investigated in lead orthophosphovanadates Pb₃(VO₄)_2(1−x)(PO₄)_2x. It was found that rich-vanadium compounds such as Pb₃(VO₄)₂ and Pb₃(VO₄)_1.6(PO₄)_0.4 densify rapidly with important grain growth. For these compounds grain growth is controlled by grain boundaries and densification occurs by a mixed mechanism with lattice and grain boundary diffusion. For Pb₃(PO₄)₂, sintering mechanism supports a model of grain-boundary-controlled densification and grain growth is a surface diffusion-controlled pore drag mechanism. Moreover, the presence of phosphorus in compounds' formulae, tends to decrease the grain-boundary mobility, preventing pore-boundary separation. The kinetics analysis highlights the importance of vanadium substitution in modifying the diffusion coefficient of rate-limiting species.     

阴极材料用Pr_(0.6–x)Nd_xCa_0.4FeO_(3–δ)陶瓷的特性

以Pechini法合成了ABO3型钙钛矿结构的Pr0.6-xNdxCa0.4FeO3-δ(x=0.1,0.3,0.5)系列稀土复合氧化物粉体。用Fourier变换红外光谱和激光共焦Raman光谱对粉体烧结后样品的化学键及物相进行了表征。用热膨胀仪测定烧结样品的热膨胀系数。通过扫描电镜观察样品用作阴极材料时的微结构及阴极/电解质[钐掺杂氧化铈(samarium-doped ceria,SDC)]复合层的断口形貌。结果表明:1200℃煅烧2h的样品的主晶相为正交钙钛矿,x=0.3的样品是正交与立方相的混合晶。在室温～1000℃范围内,烧结样品的平均热膨胀系数为12.76×10-6/K,与SDC及La0.8Sr0.2Ga0.85Mg0.15O3-δ(LSGM)电解质的热膨胀系数一致。烧结样品内部孔隙分布均匀,孔隙率约35%,阴极/电解质复合层界面清晰。将复合氧化物粉体和SDC在1200℃煅烧10h没有检测出第三相。