Molecular dynamics simulation of ion selectivity traits of nickel hexacyanoferrate thin films

The ion selectivity of nickel hexacyanoferrate thin film to alkali cations in ESIX （electrochemically switched ion exchange） processes was investigated using molecular dynamics（MD） techniques; water and cation （Na^＋ and Cs^＋） intercalation, configuration, and dynamics in reduced nickel hexacyanoferrate structures with different cation combinations were studied and compared with the experimental results. In the simulations, water was represented by an extended simple point-charge（SPC/E） model, and all other atomic interactions were represented by a universal force field（UFF）. The potential energies of various cations combination （Cs^＋ and Na^＋） in reduced i-NiHCF and 1 mol/L Cs/NaCl mixed solution were obtained. In most cases, the total potential energy of the solid is reduced when water is intercalated into the various reduced NiHCF structures. Combining the solid and the solution simulation results, it is shown that the solid composition of 3Cs^＋/1Na^＋ is the stablest structure form （NaCs3Ni4[Fe（CN）6]3） over a range of solution compositions.     

Preparation and properties of PAn/ATTP/PE conductive composites

Polyaniline/Attapugite/PE（PAn-ATTP/PE）composites containing particles with core-shell structure were obtained via the two-step blending processs. The experimental condition is as follows： Organo-attapulgite and PAn was obtained by modifying attapulgite with laury benzenesulfonic acid sodium salt and, then added to PE. The electrical conductivity, structure and properties of the composites were studied. Under the function of shear stress, core-shell structure particles with ATTP as the core and PAn as the shell were formed in the composites. The structure of PAn-ATTP/PE composites were characterized by FTIR,XRD,SEM, etc, respectively. The effects of concentration of doping agent on the conductivity and mechanical property of the composites were investigated. The mechanical properties and impact fracture surface of the ternary composites were studied by means of the tensile tester, SEM, etc. The results show that polyaniline encapsulated ATTP enhances the strength of the PE. And the conductivity of PAn-ATTP/PE composites of is improved effectively when polyaniline encapsulated ATTP is added. The composite have good conductivity when 10% polyaniline encapsulated ATTP is added.     

Preparation of novel core-shell nanoparticles by electrochemical synthesis

Nanostructural gold/polyaniline core/shell composite particles on conducting electrode ITO were successfully prepared via electrochemical polymerization of aniline based on 4-aminothiophenol （4-ATP） capped Au nanoparticles. The new approach to the fabrication included three steps： preparation of gold nanoparticles as core by pulse electrodeposition; formation of ATP monolayer on the gold particle surface, which served as a binder and an initiator; polymerization of aniline monomer initiated by ATP molecules under controlled voltage lower than the voltammetric threshold of aniline polymerization, which assured the formation of polyaniline shell film occurred on gold particles selectively Topographic images were also studied by AFM, which indicated the diameter of gold nanoparticles were around 250 run. Coulometry characterization confirmed the shell thickness of polyaniline film was about 30 nm A possible formation mechanism of the Au/polyaniline core-shell nanocomposites was also proposed. The novel as-prepared core-shell nanoparticles have potential application in constructing biosensor when bioactive enzymes are absorbed or embedded in polyaniline shell film.     

Relationships between Pitzer＇s ion interaction coefficients and ionic parameters of electrolyte solutions

Pattern recognition methods were used to treat the experimentally measured data of Pitzer‘s coefficients of 107 electrolytes, to find the relationships between the ionic structural parameters of these electrolytes and Pitzer‘s coefficients. It is found that these relationships can be approximately expressed as linear equations of four dimensionless numbers, (R /R_), (R R_)/Z Z_, (Z /Z_) and (Rt/R1), whereR and R_ are the cationic and anionic radii respectively; Z and Z_ are the cationic and anionic charge numbers respectively, and (Rt/R1) denotes the nonsphericity of some non-spherical ions. Besides, it is found that the difference of the nuclear magnetic resonance measured rotational relaxation time of water molecules around cations and anions, |△Ar| , has good correlation with Pitzer‘s coefficients. The relationships can be interpreted by the theory of corresponding states of ionic solutions. Based on the relationships, an example of application to some hydrometallurgical process was discussed.     

Preparation and properties of （K0.5Na0.5）NbO3-LiNbO3 ceramics

The lead-free piezoelectric ceramics （1-x）（K0.5Na0.5）NbO3-xLiNbO3（abbreviated as KNLN） were synthesized by a traditional solid state reaction. The effects of Li^＋ on the sintering characteristic, the phase structure and piezoelectric properties of KNLN ceramics were investigated. The sintering temperature of KNN-based ceramics is decreased by doping Li^＋ and the range of the sintering temperature is narrow. The KNLN ceramics exhibit an enhanced piezoelectric properties with the piezoelectric constant d33 value of 180-200 pC/N, The electromechanical coupling coefficients kp is 35%-40%. The results show that （1-x）（K0.5Na0.5）-NbO3-xLiNbO3 （x=0.05, 0.06） is a promising high-temperature lead free piezoelectric ceramic.     

Degradation of corrosion resistance of Zircaloy-4 in LiOH aqueous solution

To investigate the degradation of corrosion resistance of Zircaloy-4 in LiOH aqueous solution, SIMS (secondary ion mass spectrometry) analysis was performed to examine the profiles of Li^ , K^ , and OH^- in oxide layers formed in the same concentration (0.1 mol/L) LiOH and KOH solutions. Even though the oxide layers have an equal thickness, the penetration depth of K^ is shallower than that of Li^ , and the penetration depth of OH^- corroded in KOH solution is also shallower than that corroded in LiOH solution. It shows that the diffusion of OH^- into oxide layer is accompanied by the corresponding cation. The difference of degradation effect of LiOH and KOH solutions on the corrosion resistance of Zircaloy-4 was discussed.     

Synthesis and electrochemical properties of Al-doped LiVPO4F cathode materials for lithium-ion batteries

Al-doped LiVPO4F cathode materials LiAlxV1-xPO4F were prepared by two-step reactions based on a car-bothermal reduction （CTR） process. The properties of the Al-doped LiVPO4F were investigated by X-ray diffraction （XRD）,scanning electron microscopy （SEM）,and electrochemical measurements. XRD studies show that the Al-doped LiVPO4F has the same triclinic structure （space group p-↑1 ） as the undoped LiVPO4F. The SEM images exhibit that the particle size of Al-doped LiVPO4F is smaller than that of the undoped LiVPO4F and that the smallest particle size is only about 1 μm. The Al-doped LiVPO4F was evaluated as a cathode material for secondary lithium batteries,and exhibited an improved reversibility and cycleability,which may be attributed to the addition of Al^3＋ ion by stabilizing the triclinic structure.     

Preparation of Y2O3：Eu^3＋ phosphor by molten salt assisted method

A kind of fine and quasi-spherical Y2O3：Eu^3＋ phosphor was prepared by firing a preparative precursor at 1 200 ℃ for 2 h with the molten salts of Na2CO3, S and NaCl. The precursor was obtained by homogeneous precipitation of yttrium and europium with oxalic acid when using EDTA, citric acid or starch as complexant. The structure and morphology of the phosphors were characterized by XRD and SEM, respectively. The influence of complexing environment, firing temperature and molten salts on formation of the phosphor Y2O3：Eu^3＋ was discussed. The result show that the prepared Y2O3：Eu^3＋ phosphor is of quasi-spherical structure with size of 2-3 μm. Its luminescent intensity is 30% higher than that of the same phosphor prepared by the same procedure but without molten salts, and is 5% higher than that of commercial Y2O3：Eu^3＋ red phosphor.     

Effect of substrate temperature on structural properties and photocatalytic activity of TiO2 thin films

Titanium dioxide （TiO2） films with anatase structure were prepared on quartz glass substrates by pulse laser ablating titanium （99.99%） target under oxygen pressure of 10 Pa at substrate temperature of 500-800 ℃. The structural properties of the films were characterized by X-ray difffactometry（XRD）, X-ray photoelectron spectroscopy（XPS） and field emission scan electron microscopy（FESEM）. The results show that, as the substrate temperature is increased from 600 ℃ to 800 ℃, the anatase structure of the films changes from random growth to （211）-oriented growth. The absorption edge tested by UV-Vis Spectrometer has a blue shift. The photocatalytic activity of the films was tested on the degradation of methyl orange. It is found that the film with random growth structure exhibits better photo-degradation efficiency than that with （211）-oriented growth structure.     

Preparation of cobalt-modified magnetite and its magnetic properties

Magnetite was modified by reaction with alkaline solution containing Co^2 and Fe^2 to obtain a cobalt ferrite layer on the surface of particles. The influences of modification conditions on the properties were investigated. The as-prepared particles were characterized by X-ray diffraction(XRD) and transmission electron microscope(TEM). The results show that pH value influences the particles composition directly, the desirable CoFe2O4 is obtained as pH value is 12. The coercivity of particles increases with the increase of cobalt content, and the cobalt efficiency reaches a maximum value at cobalt content of 2.71% (mass fraction). With cobalt modification, the magnetite particles have the similar lattice constant and structure to that without cobalt modification, and the squareness ratio is almost 0.5. The increase of the coercivity is attributed to the uniaxial magnetic anisotropy and magnetocrystalline anisotropy of cobalt-ferrite itself.     

高能球磨辅助固相法制备Zr掺杂的钛酸锂

采用改进的高温固相法合成Zr4+掺杂的Li4Ti5O12,研究了原位包覆技术、高能球磨和金属元素掺杂对其晶型、相结构、颗粒形貌以及电化学性能的影响。结果表明:改进后的高温固相法能有效阻止颗粒团聚、提升颗粒的均匀分散度;Zr4+掺杂能降低电极极化、提升锂离子扩散系数,从而改善电化学性能。所得Li4Ti4.95Zr0.05O12在0.5 C倍率下首次放电比容量达176 mAh·g-1,在40 C高倍率下仍达52 mAh·g-1。另探讨了不同离子半径的Zr4+和Ce4+对掺杂效果的影响,结果表明较小离子半径的元素掺杂效果较好。     

Establishment of water quality index （Na^＋, Ca^2＋） for purified water reused to zinc electrolysis process

The effects of Na+ and Ca2+ in the purified water on the conductivity of zinc electrolyte and the current efficiency of zinc electrolysis were studied by the alternating current bridge method and the simulated electrolysis experiments, and the water quality index of reused water was established. The results show that the conductivity of the solution and the current efficiency decrease as these two kinds of positive ions are added in the electrolyte. The effect of Ca2+ is much more remarkable than that of Na+. ρ(Na+)≤ 8 g/L and ρ(Ca2+)≤20 mg/L are the quality indexes in the zinc electrolysis process and the concentrations of Na+ and Ca2+ in the purified water reused to the process should be less than the limited values, i.e. the water quality index of the purified water should be controlled by its reused amount.     

Li3+xV2(PO4)3的合成及电化学性能研究

通过碳热还原法合成了化学计量比的Li3V2(PO4)3和富锂的锂离子电池正极材料Li3+xV2(PO4)3(x=0.02,0.04,0.05,0.06).利用XRD、SEM和电化学测试对Li3+xV2(PO4)3进行研究表明:所合成的试样均为单斜晶系结构,无杂相存在;SEM测试发现,掺锂可以明显改善Li3V2(PO4)3一次颗粒表面的结构和形貌;电化学性能测试表明,随着掺锂量的提高,试样的循环性能变好.通过研究发现,Li3.04V2(PO4)3具有较高的初始容量和良好的循环性能.     

A-site-disorder-dependent magnetocaloric properties in the mono-valent-metal doped La0.7Ca0.3MnO3 manganites

The influence of mono-valence-metal (Li, Na, and K) doping effect on the structural, resistivity, magnetic and magnetocaloric properties of La_0.7Ca_0.3MnO₃ polycrystalline samples is studied for a fixed (5% at Ca site) dopant concentration. All the samples crystallize in orthorhombic structure and the lattice parameters increase continuously as the dopant atoms changes from Li to Na and then K. Paramagnetic-ferromagnetic phase transition at T_C and insulator-metal phase transition at T_p are observed for all studied samples. The transition temperature decreases as Ca atoms is replaced by Li, while the transition temperature shifts to higher values as Ca is substituted by Na or K. In addition, the maximum magnetic entropy change of the K-doped sample is much smaller than that of the free- and Na-doped samples. The results are discussed according to the change of A-site-disorder effect caused by the systematic variations of A-site average ionic radius 〈r_A〉 and A-site-cation mismatch σ².     

Li3PO4对Li0.5La0.5TiO3/Li3PO4复合固体电解质的电性能影响

利用复阻抗谱分析技术考察了复合Li3PO4的Li0.5La0.5TiO3 (LLTO) 固体电解质的离子电导率,同时还利用X射线衍射图谱、扫描电镜观测和相对致密度测量等实验手段研究了LLTO电解质中第二相的分散情况。结果发现,加入Li3PO4第二相后,尽管复合固体电解质LLTO拥有比较高的致密度,但是Li3PO4会导致离子电导率的降低。通过分析LLTO的晶体结构,晶界的微观结构和锂含量,阐明了LLTO离子电导率恶化的原因,往LLTO基质中分散的Li3PO4导致的锂含量和微观结构的变化是引起锂离子传导行为改变的主要原因。     

柠檬酸凝胶燃烧法制备Nd、Yb:GGG纳米多晶粉体

以Nd2O3、Yb2O3、Gd2O3和Ga2O3为原料,采用柠檬酸凝胶燃烧法制备了Nd3xYb3yGd(3-3x-3y)Ga5O12(Nd、Yb:GGG)纳米多晶粉体。利用XRD、IR、SEM及荧光光谱研究了Nd、Yb:GGG纳米多晶粉体的相组成及荧光性能。XRD测试结果表明,粉体在未煅烧时已结晶,煅烧温度为700℃时粉体已形成Nd、Yb:GGG纯相;SEM观察发现,Nd、Yb:GGG纳米多晶粉体粒度约为50nm,粒径均匀,分散性较好。荧光光谱测试结果表明,Nd、Yb:GGG纳米多晶粉体最强发射峰在1030nm,是Yb3+的2F5/2-2F7/2谱项导致的荧光发射,未发现Nd3+的荧光发射峰,说明Nd3+将吸收的能量传递给了Yb3+。     

Electrochemical polymerization of aniline on aluminum electrode from an oxalic acid and H2SO4 solutions

In this study, the polymerization of aniline on Al and Pt electrode was examined by cyclic voltammetry There had been reversible reaction on Al electrode. But on the other hand there had been irreversible reaction on Pt electrode. The addition of aniline into the solution led the decrease of current values. The current decreased by adsorption of anodic products on polymer surface. The fact that the anodic peak potential shifted to positive value shows that polyaniline (PANI) catalyzed the formation of polymer. This case shows that the aniline shifted the electrode potential to positive side by the adsorption on the surface. When Al electrode covered with polymer (in 50 mV s⁻¹ potential scanning rate after 20 cycles) was immersed into 1 N HCl solution, the inorganic layer decomposed on the metal surface. This led to decrease the polarization resistance of the metal. SEM microphotographs and EDX fingerprints also confirmed these results.     

Molten salt phase diagram evaluation by pattern recognition：Part I Divalent rare earth halide and alkali metal halide binary systems

At present CALPHAD (CALculation of PHAse Diagram) technique is not capable of predicting whether there exists intermediate compound, much less predicting the formulae, the number, and the melting congruence of intermediate compounds. To solve this problem, a new approach called the phase diagram evaluation by pattern recognition (PDEPR) was improved. The micro-parameters, such as the radius and the electronegativity of the element, were used as original features and then they were transformed and spanned to the different features in multi-dimensional space. Then a set of classifying functions were obtained to predict the information of intermediate compounds in REX2-AX systems (RE-rare earth element; A--Li, Na, K, Rb, and Cs; X--F, CI, Br, and I). It is comparatively important for the design of materials.     

Effects of Adding Sodium and Ethanol Inhibitor on Inhibiting H2 Evolution of Lithium Anode

在30℃的4mol/LLiOH电解质溶液中,通过测量锂负极的自腐蚀析氢速率、极化曲线、电化学阻抗谱及电位-时间曲线,研究了Na作为合金元素及乙醇作为添加剂对锂负极的共同抑制自腐蚀析氢作用。结果表明:合金元素Na及乙醇对阴阳极反应都起到了抑制作用,但是单一添加合金元素Na或者乙醇缓蚀剂对锂负极的抑氢作用不大,而当共同添加合金元素Na及乙醇时对锂负极的抑氢效率提高明显,缓蚀率超过了80%。另外,单独添加合金元素Na时,锂负极的放电性能极不稳定,而溶液中添加乙醇后有利于提高锂负极的放电稳定性。XRD结果表明,钠与锂形成了比较理想的固溶体。