Structural modulation and physical properties of cobalt-doped layered La_2M_5As_3O_2(M=Cu,Ni) compounds

We investigate the structural variation and physical properties of layered La_2M_5As_3O_2(M=Cu,Ni) compound upon Co doping. It is found that the substitution of Co ion just induces the monotonous change of lattice constants without observing the anomalous kink in superconducting La_2(Cu~(1-x)Nix)_5 As_3O_2 solid-solutions. Meanwhile, this doping barely changes As–As bond length in [M_5As_3]~(2-) subunit(±2%), being significantly smaller than 7% shrinkage of that in La_2(Cu~(1-x)Nix)_5 As_3 O_2. Therefore, the doping dependence of crystal structure exhibits similar trend with Ba~(1-x)K_xFe_2 As_2 without the interference of As1–As 2 bonding, implying that the Co substitution for Cu/Ni is hole-doped. In terms of physical property, La2(Cu1-xCox)~5As_3O_2 turns into itinerant ferromagnetic metal, while La2(Ni1-x Cox)5 As3 O2 shows paramagnetism and suppressed structural phase transition upon Co-doping. The distinct structural variation and absence of superconductivity provide important clues to understand the effect of As–As bond in [M_5 As_3]~(2-) subunit.     

Effect of aliovalent ion substitution on the oxide ion conductivity in rare-earth pyrohafnates RE2−xSrxHf2O7−δ and RE2Hf2−x AlxO7−δ (RE=Gd and Nd; x=0, 0.1 and 0.2)

Oxide ion conductivity of the pure and aliovalent ion substituted rare-earth pyrohafnates in the series RE_2−xSr_xHf₂O₇ and RE₂Hf_2−xAl_xO₇ (RE=Gd and Nd; x=0–0.2) has been explored in the temperature range 400°C–700°C for the first time. It is seen that, conductivity is enhanced by doping 5 atom% Sr at the rare–earth site in these systems. Well defined impedance plots due to grain interior and grain boundary resistances were obtained in the Gd pyrohafnate with Sr substitution. The results of the conductivity variation for the pure, Sr and Al doped phases are explained on the basis of pyrochlore structure.     

Na+替位掺杂对Li2MnSiO4的电子结构以及Li+迁移过程的影响

在锂二次电池中, 硅酸锰锂作为正极材料得到广泛研究, 但其固有的电子和离子电导率较低, 直接影响着电池的功率密度和充放电速率. 本文建立了不同浓度的Na⁺离子替位掺杂Li⁺离子形成的Li_1-xNa_xMnSiO₄(x=0, 0.125, 0.25, 0.5)结构, 采用第一性原理的方法, 研究了掺杂前后硅酸锰锂的电子结构以及Li⁺离子的跃迁势垒. 发现在Li⁺位替代掺杂Na⁺, 导带底的能级向低能方向发生移动, 降低了Li₂MnSiO₄ 材料的禁带宽度, 有利于提升材料的电子导电性能. 随着掺杂浓度的升高, 禁带宽度逐渐变窄. CI-NEB结果表明, 在Li₂MnSiO₄体系中具有两条有效的Li⁺离子迁移通道, 掺杂Na⁺以后扩大了Li⁺ 离子在[100]晶向上的迁移通道, Li⁺离子的跃迁势垒由0.64 eV降低为0.48, 0.52和0.55 eV. 掺杂浓度为 x=0.125时, 离子迁移效果最佳. 研究表明Na⁺掺杂有利于提高Li₂MnSiO₄材料的离子和电子电导率.     

Effect of co-doped metal caions on the properties of Y_2O_3:Eu~(3+) phosphors synthesized by gel-combustion method

Y_2O_3:Eu~(3+) phosphors co-doped with different metal cations(Li~+, Na~+, K~+, Mg~(2+), Ca~(2+)) are prepared by the gelcombustion method with Y_2O_3, Eu_2O_3, and R(NO3)x(R = Li, Na, K, Mg, Ca) serving as raw materials and glycine as fuel,calcined at 1000?C for 2h. The synthesized Y_2O_3:Eu~(3+) phosphors doped with different metal cations and doping ratios are characterized by x-ray diffractometry(XRD), fluorescence and phosphorescent spectrophotometer. The co-doping metal cations are advantageous to the development of Y_2O_3:Eu~(3+) lattice. All the samples can emit red light peaked at 611 nm under 254-nm excited. The luminescence intensities of co-doping samples are increased because the cations increase the electron transition probability of Eu~(3+) from ~5D_0 level to ~7F level. The fluorescence lifetime of Eu~(3+)(~5D_0→~7F_2) is increased by doping metal cations.     

Dip-coated silver-doped V2O5 xerogels as host materials for lithium intercalation

Vanadium pentoxide xerogels have shown high electrochemical performance in terms of energy content. The high specific energy and high intercalation capability make the materials promising for thin film lithium battery and electrochromic device applications. In order to enhance the rate capabilities of the host we increased the electronic conductivity by doping the V₂O₅ xerogels with silver. Samples were prepared by mixing various amounts of silver powder with V₂O₅ hydrogel. We were able to prepare silver-doped vanadium pentoxide dip-coated thin films with a molar ratio (Ag/V) ranging from 0.005 to 0.5 (Ag_yV₂O₃ with y = 0.01, 0.1 and 1). With the successful doping, the electronic conductivity of V₂O₅ was increased by 2 to 3 orders of magnitude. The insertion capacity of the material was maintained and up to 4 moles of lithium per mole of silver-doped V₂O₅ (XRG) were found to be reversibly intercalated.     

Oxide-ion conductivity of (Ba1−xLax)2In2O5+x system based on brownmillerite structure

(Ba_1−xLa_x)₂In₂O_5+x, whose end member is Ba₂In₂O₅, is an oxygen-deficient perovskite oxide showing high oxide-ion conductivity. In order to clarify the reason why the high oxide ion conductivity appeared in this system, the electrical conductivity was measured as a function of temperature and La content. With an increasing La content, the discontinuous jump of ion conductivity in the Arrhenius plot, which is related to the disordering of the oxygen vacancies, disappeared for the sample with x0.2. Above x=0.12, the ion conductivity linearly increased with La content, while the activation energy remained constant with respect to the La content. Moreover, the conductivity for x=0.6 was 0.042 (S/cm) at 1073 K, which exceeded that of 8 mol% yttria-stabilized zirconia. The higher oxide-ion conductivity of this system could be dominated by the amount of mobile oxygen ions.     

Niobium based tetragonal tungsten bronzes as potential anodes for solid oxide fuel cells: synthesis and electrical characterisation

In this paper we report studies on a range of niobate based tungsten bronzes, with a view to analysing their potential as anode materials in SOFCs. Six systems were studied, (Sr_1−xBa_x)_0.6Ti_0.2Nb_0.8O₃, Sr_0.6−xLa_xTi_0.2+xNb_0.8−xO₃, (Sr_0.4−xBa_x)Na_0.2NbO₃, (Ba_1−xCa_x)_0.6Ti_0.2Nb_0.8O₃, Ba_0.5−xA_xNbO₃ (A=Ca, Sr), and Ba_0.3NbO_2.8, and the electrical conductivities were examined over a range of oxygen partial pressures (10⁻²⁰–1 bar). All the systems showed good conductivity in low oxygen partial pressures, with values as high as 8 S cm⁻¹ at 930°C (P(O₂)=10⁻²⁰ bar). As the oxygen partial pressure was raised the conductivity dropped showing in most cases an approximate [P(O₂)]^−1/4 dependence and good re-oxidation kinetics. Of all the samples studied the (Sr_1−xBa_x)_0.6Ti_0.2Nb_0.8O₃ and (Ba_1−xCa_x)_0.6Ti_0.2Nb_0.8O₃ systems appear most promising for potential use as anode materials in SOFCs.     

Molecular dynamics analysis of impurity ions behavior in β″-Al2O3

The effects of foreign impurity ions in the conduction plane on the β″-Al₂O₃ lattice have been analyzed by molecular dynamics. As impurity ions, K and Ca ions were chosen and Na sites in the conduction plane were replaced with these ions. Results are summarized as follows: (1) The β″-Al₂O₃ lattice expands perpendicular to the conduction plane when K ions are doped; (2) Ca ions do not contribute to expansions of the β″-Al₂O₃ lattice; (3) both K and Ca ions reduce the mean square displacement of Na ions, which can be attributed to decreased Na ion diffusion.     

钙钛矿锰氧化物(La_(1-x)Eu_x)_(4/3)Sr_(5/3)Mn_2O_7(x=0,0.15)的磁性和电性研究

通过传统固相反应法制备了钙钛矿锰氧化物(La1-xEux)4/3Sr5/3Mn2O7(x=0,0.15)多晶样品,并且对其磁性和电性进行了研究.磁性测量表明:随着温度的降低,样品经历了一个复杂的转变过程,在温度为T*时经历二维短程铁磁有序转变,在温度为TC时进入三维长程铁磁态.随着Eu的掺杂,T*和TC减小,并且样品(La0.85Eu0.15)4/3Sr5/3Mn2O7在低温区表现出自旋玻璃行为.电性质测量表明:在母体La4/3Sr5/3Mn2O7中La位掺杂Eu后电阻率明显变大,金属绝缘转变温度TMI降低,磁电阻峰值增大.这些影响归因于较小的Eu3+离子替代La3+离子导致平均离子半径减小,晶格发生畸变.此外,较小的Eu3+离子优先占据层间岩盐层的R-site,使La3+,Sr3+,Eu3+离子在(La0.85Eu0.15)4/3Sr5/3Mn2O7中的分布更加有序,所以x=0.15的样品的ρ-T曲线只有一个峰.     

Designing a P2-type cathode material with Li in both Na and transition metal layers for Na-ion batteries

P2-type layered oxides have been considered as promising cathode materials for Na-ion batteries, but the capacity decay resulting from the Na⁺/vacancy ordering and phase transformation limits their future large-scale applications. Herein, the impact of Li-doping in different layers on the structure and electrochemical performance of P2-type Na_0.7Ni_0.35Mn_0.65O₂ is investigated. It can be found that Li ions successfully enter both the Na and transition metal layers. The strategy of Li-doping can improve the cycling stability and rate capability of P2-type layered oxides, which promotes the development of high-performance Na-ion batteries.     

Observation of giant magnetocaloric effect under low magnetic fields in EuTi_(1-x)Co_xO_3

The magnetic properties and magnetocaloric effect(MCE) in EuTi_(1-x)Co_xO_3(x = 0, 0.025, 0.05, 0.075, 0.1) compounds have been investigated. When the Ti~(4+) ions were substituted by Co2+ions, the delicate balance was changed between antiferromagnetic(AFM) and ferromagnetic(FM) phases in the EuTiO_3 compound. In EuTi_(1-x)Co_xO_3 system, a giant reversible MCE and large refrigerant capacity(RC) were observed without hysteresis. The values of -?S_M~(max) were evaluated to be around 10 J·kg~(-1)·K~(-1) for EuTi_(0.95)Co_(0.05)O_3 under a magnetic field change of 10 kOe. The giant reversible MCE and large RC suggests that EuTi_(1-x)Co_xO_3 series could be considered as good candidate materials for low-temperature and low-field magnetic refrigerant.     

Improvement of electrochemical properties of the spinel LiMn2O4 using a Cr dopant effect

A series of LiCr_xMn_2−xO₄ spinels were synthesised by the Pechini method which enables dopant Cr ions to distribute at Mn sites homogeneously. Neutron diffraction and EDS analysis confirmed that Cr ions do occupy 16d sites (octahedral intestial) evenly in the spinel structure. The Cr dopant effect improves the cyclability of spinel LiMn₂O₄ electrodes and decreases the self-discharge rate substantially. Cyclic voltammetry and AC impedance spectroscopy were employed to characterise the reactions of lithium insertion into and extraction from LiCr_xMn_2−xO₄ electrodes. It was found that a thicker surface layer was formed on the surface of the pure LiMn₂O₄ electrode than on the LiMn₂O₄ electrode.     

Ionic conduction properties of layer-type oxides NaxMx/2Ti1−x/2O2 (M=Ni, Co; 0.60≤x≤1.0)

Layer-type oxide Na_xM_x/2^IITi_1−x/2^IVO₂ (M=Co, Ni; 0.60≤x≤1.0) has been prepared by solid state reactions. In both series, two structural variants of type -NaFeO₂ (O3) and β-RbScO₂ (P2) have been obtained consecutively as x decreases with a borderline composition around x_c0.7. With the decrease of x, the ionic conductivity has been found to increase up to 8.4×10⁻² S cm⁻¹ at 770 K (Na_0.67Co_0.33Ti_0.67O₂). Compositions of P2 have been found to exhibit the conductivity values two to five times greater than those of O3, primarily due to the larger rectangular threshold available for the diffusion of Na⁺ ions. Such a structural effect has also been considered to depend on the polarizability of alkali ion. HT-XRD and ²³Na-NMR data of Na_0.67Co_0.33Ti_0.67O₂ strongly suggest that the diffusion of Na⁺ ion is deeply related with the local distortion of trigonal prismatic sites, leading to the change of activation energy around 430 K.     

Crystal structure, superconductivity and magnetic properties of the superconducting ferromagnets Gd1.4−xDyxCe0.6Sr2RuCu2O10 (x=0–0.6)

The structural, electrical and magnetic properties of the superconducting ferromagnets, Gd_1.4−xDy_xCe_0.6Sr₂RuCu₂O₁₀ (x=0–0.6) are systematically investigated as a function of Dy doping and temperature. These compounds are characterized by high temperature superconductivity (T_c ranging from 20 to 40 K depending upon the Dy content) co-existing with weak ferromagnetism with two magnetic transitions (T_M2 ranging from 95 to 106 K and T_M1 around 120 K). Doping with Dy gives no significant structural changes except for a minor change in the c/a ratio. However the superconducting transition temperature is significantly suppressed and magnetic ordering temperature enhanced on Dy doping. These effects are described and discussed.     

Oxygen diffusion and surface exchange in La1−xSrxFe0.8Cr0.2O3−δ (x=0.2, 0.4 and 0.6)

Oxygen tracer diffusion (D*) and surface exchange rate constant (k*) have been measured, using isotopic exchange and depth profiling by secondary ion mass spectrometry (SIMS), in La_1−xSr_xFe_0.8Cr_0.2O_3−δ (x=0.2, 0.4 and 0.6). Measurements were made as a function of temperature (700–1000 °C) and oxygen partial pressure (0.21–10⁻²¹ atm) in dry oxygen, water vapour and water vapour/hydrogen/nitrogen mixtures. At high oxygen activity, D* was found to increase with increasing temperature and Sr content. The activation energies for D* in air are 2.13 eV (x=0.2), 1.53 eV (x=0.4) and 1.21 eV (x=0.6). As the oxygen activity decreases, D* increases as expected qualitatively from the increase in oxygen vacancy concentration. Under strongly reducing conditions, the measured values of D* at 1000 °C range from 10⁻⁸ cm² s⁻¹ for x=0.2 to 10⁻⁷ cm² s⁻¹ for x=0.4 and 0.6. The activation energies determined at constant H₂O/H₂ ratio are 1.21 eV (x=0.2), 1.59 eV (x=0.4) and 0.82 eV (x=0.6).

The surface exchange rate constant of oxygen for the H₂O molecule is similar in magnitude to that for the O₂ molecule and both increase with increasing Sr concentration.     

The role of Bi2O3 as a network modifier and a network former in xBi2O3 · (1 − x)LiBO2 glass system

The effect of Bi₂O₃ on the glass transition temperature, electrical conductivity and structure of LiBO₂ glass has been investigated. T_g vs. composition curve shows three different linear regions, while there is an overall decrease in T_g with the increase in Bi₂O₃ content. The slope of these three straight lines is in a decreasing order. These results are interpreted in terms of the increase in the number of non-bridging oxygen atoms, substitution of Bi-O bond in place of B-O bond and change in Li⁺ ion concentration. The conductivity vs. composition curve exhibits two maxima which are interpreted in terms of the structural modification effect of Bi₂O₃ on LiBO₂ network and mixed-former effect, respectively. Results obtained from the XPS studies of the samples of composition x 0.005, have shown that the number of non-bridging oxygen atoms from B-O bond increases with the increase in Bi₂O₃ content. It has a maximum value at x = 0.003 where the conductivity has also exhibited a maximum value. Further increase of Bi₂O₃ content causes decrease in it. For higher Bi₂O₃ content (x * > 0.005), O 1s spectra of Bi₂O₃ has been separated out from that of Bi₂O₃. Bismuth ions have been substituted for boron ions as network former ions.     

Shaped crystal growth and scintillating properties of Yb:(Gd,Lu)3Ga5O12 solid solutions

Shaped single crystals of (Lu_xGd_1−x)₃Ga₅O₁₂ (0.0x1.0) and (Yb_0.05Lu_xGd_0.95−x)₃Ga₅O₁₂ (0.0x0.9) were grown by the modified micro-pulling-down method. Continuous solid solutions with garnet structure and a linear compositional dependency of crystal lattice parameter in the system Yb:(Gd,Lu)₃Ga₅O₁₂ are formed. Measured optical absorption spectra of the samples show 4f–4f transitions related to Gd³⁺ ion at 275 and 310 nm, and also an onset of charge transfer transitions from oxygen ligands to Gd³⁺ or Yb³⁺ cations below 240 nm. A complete absence of Yb³⁺ charge transfer luminescence under X-ray excitation in any of the investigated samples was explained by the overlapping of charge transfer absorption of Yb³⁺ by that of Gd³⁺ ions. For specific composition of Lu_1.5Gd_1.5Ga₅O₁₂ an intense defect-host lattice-related emission, which achieve of about 40% integrated intensity compared with Bi₄Ge₃O₁₂, was found.     

Density functional theory study of formaldehyde adsorption and decomposition on Co-doped defective CeO_2(110) surface

Formaldehyde as an air pollutant to adverse health effects for humanity has been getting attention. The adsorption and dissociation of formaldehyde(HCHO) on the Co_xCe_(1-x_O_(2-δ)(110) surface were investigated by the density functional theory(DFT) calculations. We calculated the oxygen vacancy formation energy as the function of its site around dopant Co in detail. The results showed that Co doping was accompanied by compensating oxygen hole spontaneous formation.The adsorption configurations and bindings of HCHO at different locations on the Co_xCe_(1-x)O_2(110) were presented.Four possible pathways of oxidation of formaldehyde on the catalytic surface were explored. The results suggested that formaldehyde dissociation at different adsorption sites on the doped CeO_2(110) — first forming dioxymethylene(CH_2O_2)intermediate, and then decomposing into H_2O, H_2, CO_2, and CO molecules. It was found that the presence of cobalt and oxygen vacancy significantly prompted the surface activity of CeO_2.     

The crystal structure of (Pb0.5Cd0.5)Sr2 (Y1−xCax)Cu2O7

The crystal structures of (Pb_0.5Cd_0.5)Sr₂YCu₂O₇, (Pb_0.5Cd_0.5)Sr₂(Y_0.6Ca_0.4)Cu₂O₇ and (Pb_0.5Cd _0.5)Sr₂(Y_0.5Ca_0.5)Cu₂O₇ have been refined by the Rietveld method for the X-ray diffraction data. The refinement results indicate that both Pb and Cd atoms in the (Pb, Cd)O layers and O(3) atoms are displaced from their ideal sites, and that there is a complicated occupation in the (Pb, Cd)O layers, i.e., other cations, such as Sr²⁺, Cu²⁺ and Ca²⁺, can occupy the (Pb, Cd) site for these samples. This may be the reason why the lattice constants do not vary monotanically with the calcium content, and why there exist broad superconducting transitions in the system (Pb_0.5Cd_0.5)Sr₂(Y_1−xCa_x)Cu₂O₇. The refinement results also indicate that, as the calcium content increases, the O(2) atoms move close to the CuO₂ planes and far from the (Pb, Cd)O layers. Thus, the increase of calcium content results in charge transfer from the charge reservoir layer (Pb, Cd)O to the CuO₂ planes. This result is consistent with the bond valence sums of the Cu ions in the CuO₂ planes.     

钙钛矿锰氧化物(La1-xGdx)4/3Sr5/3Mn2O7 (x=0, 0.025) 磁性和输运性质研究

采用传统的高温固相烧结法制备了双层钙钛矿锰氧化物(La_1-xGd_x)_4/3Sr_5/3Mn₂ O₇ (x=0, 0.025)多晶样品. 通过X射线衍射仪研究发现样品为Sr₃Ti₂O₇型四方结构, 空间群为I4/mmm; 磁性测量表明, Gd³⁺掺杂后的样品(La_0.975Gd_0.025)_4/3Sr_5/3Mn₂O₇的三维磁有序转变温度(T_C1^3D)、磁化强度(M)均降低, 这是由于Gd³⁺的掺杂引起晶格的畸变, 从而使得晶格常数发生改变, 减弱了铁磁耦合而导致的; 通过电子自旋共振谱测量发现, 在T_C^3D<T<300 K温度范围内, 两样品在顺磁的基体上均有短程的铁磁团簇存在, 出现了相分离现象. 电性测量表明: 两样品分别在T_C1^3D (La_4/3Sr_5/3Mn₂O₇ 样品的三维磁有序转变温度, T_C0^3D)<T<300 K温度范围内均以三维变程跳跃的方式导电, 分析得出Gd³⁺的掺杂使得载流子局域长度的减小. 这表明载流子需要吸收更多的能量才能克服晶格的束缚进行跳跃, 因此(La_0.975Gd_0.025)_4/3Sr_5/3Mn₂ O₇ 样品的电阻较高.