Li2S-P2S5玻璃陶瓷固体电解质的制备研究

利用高能球磨及随后热处理的方法制备了具有高锂离子导电性的80Li2S-20P2S5（mol%）玻璃陶瓷固体电解质。通过X射线衍射分析、扫描电镜及交流阻抗法分别研究了固体电解质的物相种类、形貌及离子电导率。研究发现,球磨时间对玻璃态的形成具有直接影响,高能球磨得到的玻璃态中间体经过热处理形成了玻璃陶瓷电解质,其中含有Li7PS6、Li3PS4以及thioLISICON类似物等晶体,晶粒之间接触十分紧密,其室温锂离子电导率较玻璃态有明显提高。     

Li2S—SiS2—LiBO2—LiCl体系玻璃的XPS表征

本文采用光电子能谱分析方法,首次研究Li_2S-SiS_2-LiBO_2-LiCl体系硫氧化物玻璃锂离子导体的组成、结构和状态。指出在该玻璃体系中,除与硅(硼)相键合的桥硫存在外,还有不与硅(硼)相键合的非桥硫存在;玻璃中的硫取代了氧的位置,进入玻璃网络中使结构紧密交联。对网络中的元素状态,成键及性能进行了讨论。     

An Intermediate-temperature H2S Fuel Cell with a Li2SO4-based Proton-conducting Membrane

A laboratory-scale intermediate-temperature H2S fuel cell with a configuration of H2S, （metal sulfide-based composite anode）/Li2SO4＋Al2O3/（NiO-based composite cathode）, air was developed and studied for production of power and for desulfurization of a fuel gas process stream. The cell was run at typical temperature （600-650℃） and ambient pressure, but its electrochemical performance may be limited by electrolyte membrane thickness. The membrane and its performance in cell have been characterized using scanning electron microscope （SEM） and electrochemical impedance spectrum （EIS） techniques. Composite anodes based on metal sulfides, Ag powder and electrolyte behaved well and stably in H2S stream, and composite cathodes based mainly on nickel oxide, Ag powder and electrolyte had superior performance to Pt catalyst. The maximum power density of up to 70mW.cm^-2 and current density of as high as 250mA.cm^-2 were obtained at 650℃. However, the long-term cell stability remains to be investigated.     

Catalytic behavior of V2O5 in rechargeable Li–O2 batteries

The possibility of using vanadium pentoxide (V₂O₅) as a catalyst in rechargeable lithium–oxygen (Li–O₂) batteries was studied. A V₂O₅-carbon composite was cast onto Ni foam to form a cathode. Electrochemical cells designed based on the flat cell manufactured by Hohsen Corporation were fabricated. The initial discharge capacity was 715 mA?h?g^?1, and the maximum discharge capacity reached 2,260 mA?h?g^?1 during the twelfth cycle. The cell had high capacity retention during cycling (1.24?% during cycles 2–8). V₂O₅ acted as a catalyst as well as an active material, improving the specific capacity and capacity retention of the non-aqueous Li–O₂ cell more effectively than do other materials.     

Phase diagram of the Li2SO4–Na2SO4 system

The thermal analysis and X-ray powder diffraction studies of the Li₂SO₄–Na₂SO₄ system, including the high-temperature X-ray diffraction technique, have elucidated four phases of variable composition: three solid solutions based on the α-Li₂SO₄, α-Na₂SO₄, and α-LiNaSO₄ high-temperature polymorphs, and a low-temperature β-LiNaSO₄ phase. α-Na₂SO₄-Base solid solution disintegrates into two phases via a monotectoid phase transformation. It is quite probable that the monotectoid process is related to the conversion of the second-order phase transition to the first-order phase transition.     

Selective absorption of H2S from CO2 — factors controlling selectivity toward H2S

A novel experimental system was adapted to determine factors controlling selective absorption of hydrogen sulfide (H₂S) from carbon dioxide (CO₂). This work demonstrates that liquid film controlled mass transfer regime and a low value of the liquid side mass transfer coefficient favors selective removal of H₂S from CO₂. By identifying the factor controlling selective removal of H₂S from CO₂, this work lays the basis for the parameter optimization of a process for selective removal of H₂S from CO₂.     

Phase formation during crystallization of a Li2O-Al2O3-SiO2 glass with ZrO2 as nucleating agent – An X-ray diffraction and (S)TEM-study

Glass ceramics based on the system Li₂O/Al₂O₃/SiO₂ (LAS) often show a coefficient of thermal expansion close to zero. Although these glass-ceramics are of high economic importance, the fundamentals of the crystallization process are still not fully understood. In this paper, the effect of ZrO₂ addition as a sole nucleation agent on the crystallization of the LAS glass is described predominantly using transmission electron microscopy and X-ray diffraction. The composition of the studied green glass was close to that of the commercially available Robax™ glass (Schott AG), which, however, contained both, ZrO₂ and TiO₂ as nucleating agents. It was found that during thermal treatment, in a first step, already at temperatures around 10–20 K below the glass transition temperature, T_g, ZrO₂ nanocrystals with sizes in the range from 5 to 15 nm were precipitated. The next crystalline phase that forms during the crystallization process was LAS with a structure similar to the hexagonal high temperature phase of quartz. These crystals were much larger than the ZrO₂ crystals. If thermal treatment was carried out at higher temperatures, a dense network of LAS crystals was formed. Differently shaped crystals in samples with different thermal history were visualized, and an enrichment of Ba and Sb in the residual glass phase in the late stages of thermal treatment was found. Also, an enrichment of aluminum around the ZrO₂ crystals was evident, which is a hint at a preceding droplet phase separation from which the ZrO₂ crystals were precipitated. The crystallization is notably different from that of mixed ZrO₂/TiO₂ nucleating agents used in commercial lithium alumosilicate glass ceramics.     

Enhanced thermoelectric efficiency of Cu2−xSe–Cu2S composite by incorporating Cu2S nanoparticles

The study of thermoelectric transport properties in Cu_2−xSe and Cu₂S has gained an importance in the thermoelectric research during last few years due to their superionic behavior and low cost. Here, we reported a facile method to enhance the thermoelectric efficiency of Cu_2−xSe by introducing Cu₂S nanoparticles (NPs) in the matrix of Cu_2−xSe. The observed efficiency is a direct result of simultaneous improvement of Seebeck coefficient (S) because of the external strain induced by Cu₂S nanoinclusions in Cu_2−xSe and decline in the total thermal conductivity by suppressing both electronic and lattice thermal contributions. Such higher S and lower thermal conductivity is realized for a composite structure with 10 wt% nanoinclusions of Cu₂S which effectively contributed to higher ZT value of 0.90 at moderate temperature of 773 K. Thus, it is believed that the proposed hybrid structure is a promising p-type thermoelectric material for mid-temperature range energy harvesting applications.     

Preparation and characterization of Co2+ substituted Li–Dy ferrite ceramics

Stoichiometric compositions of ferrites with the chemical formula Li_0.5?0.5xCo_xFe_2.4?0.5xDy_0.1O₄ with x=0, 0.25, 0.5, 0.75, 1.0 were prepared by the standard double sintering ceramic method. X-ray diffraction analysis confirmed the cubic spinel structure of the prepared samples. The structural, morphological and magnetic properties were studied by X-ray diffraction, infra-red spectroscopy (IR), scanning electron microscopy (SEM), vibrating sample magnetometry (VSM) and ac susceptibility measurements. Lattice constant, grain size and density increase whereas porosity decreases with the increase in Co²⁺ substitution. IR measurements show the characteristic ferrite bands. Spectral absorption bands were observed in IR spectroscopic analysis at ν₁=564?601 cm^?1, ν₂=486?519 cm^?1 and ν₃=551?578 cm^?1. The cation distribution estimated by the X-ray diffraction is supported by magnetization and susceptibility studies. The saturation magnetization decreases from 44.25 to 17.14 emu/g whereas coercivity remarkably increases from 240.69 to 812.14 emu/g with increasing Co²⁺ substitution. The mechanisms involved are discussed.     

Research of positron annihilation and hydration of doped β-C2S

The lifetime spectrum of positron in β-C₂S of added Na₂O or P₂O₅ is studied with positron annihilation technique. According to the theory of the capture of positron, we discuss the relationship between lifetime spectrum parameters obtained through experiment and the microstructure of β-C₂S. The results show that the long living component τ₂ (about 470 ps) represents the capture of positron in the defects of Ca²⁺ vacancies and that the intensity of I₂ of τ₂ decreases with the increasing of Na⁺ and increases with the increasing of P⁵⁺. The results also verify that Na⁺ replaces Ca²⁺ and creates anion vacancies; while P⁵⁺ replaces Si⁴⁺ and creates cation vacancies. Vacancy concetration increases Na⁺ and P⁵⁺. Our work shows that the positron annihilation technique is a useful tool for studying the change of microstructure defects in doped β-C₂S. The relationship between heat treatment and hydration activity of doped β-C₂S and its impurities are also studied and discussed.     

Microwave dielectric properties of low-fired Li2MnO3 ceramics co-doped with LiF–TiO2

Li₂MnO₃ ceramics co-doped with 2 wt% LiF and x wt% TiO₂ (x=0, 3, 5, 7, 10) were prepared by solid-state reaction for low-temperature co-fired ceramics (LTCC) applications. The sintering temperatures of Li₂MnO₃ ceramics were successfully lowered to 925°C due to the formation of a LiF liquid phase. Their temperature stability was improved by doping with TiO₂. A typical Li₂MnO₃-2 wt% LiF-5 wt% TiO₂ sample with well-densified microstructures displayed optimum dielectric properties (ε_r=13.8, Q×f= 23,270 GHz, τ_f=1.2 ppm/°C). Such sample was compatible with Ag electrodes, which suggests suitability of the developed material for LTCC applications in wireless communication systems.     

Li2O-CuO-P2O5玻璃的电性能

本文采用一种新的成形工艺制备20Li2O-30CuO-50P2O5(摩尔比)玻璃,并在玻璃转变温度之上对样品进行了不同时间的热处理后测试了其电性能。结果发现,随热处理时间的延长电导率会出现峰值,且所有样品电导率与温度之间的关系都能很好地遵从Arrhenius关系,结合SEM、XPS和XRD分析,对这一现象作出了初步的解释。     

Li2O对近零膨胀Li2O-Al2O3-SiO2透明微晶玻璃性能的影响

以Li2O-Al2O3-SiO2(LAS)系微晶玻璃为研究对象,采用示差扫描量热(DSC),X射线衍射分析(XRD),扫描电镜(SEM)等测试方法研究不同Li2O含量锂铝硅透明微晶玻璃的相转变及其各项性能.结果表明,随着Li2O含量的增加,玻璃的熔化温度降低,熔化质量提高,析晶峰温度降低.热处理后的玻璃试样,随着Li2O含量的增加,主晶相由LixAlxSi3-xO6逐渐转变为LiAlSi2O6,颗粒尺寸变大,热膨胀系数变大,化学稳定性提高,透明性变差.     

Solid-state formation of lithium ferrites from mechanicallyactivated Li2CO3–Fe2O3 mixtures

The formation of lithium ferrites (LiFe₅O₈ and LiFeO₂) from mechanically activated mixtures of Li₂CO₃–Fe₂O₃ has been studied using thermal analysis (TGA, DSC), evolved gas analysis (TG/FT-IR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and particle size analysis. It is shown that mechanical activation of the precursors considerably enhances the reactivity of the solid system analysed and makes it possible to obtain reaction products with a much lower expense of thermal energy. In particular, lithium ferrites can be obtained at temperatures at least 160 °C lower than those necessary in the absence of mechanical activation. Moreover, both the microstructure and the allotropic ratio of the products, as well as the reaction path, are affected by mechanical activation.     

Quantitative prediction of the structure and properties of Li2O–Ta2O5–SiO2 glasses via phase diagram approach

Tantalum silicate glasses serve as laser host materials to take advantage of their high refractive index and the ability to tailor their physical properties in the design of high-performance photonic and photoelectric components. However, successful attainment of feature control in tantalum-doped materials remains a longstanding problem due to the limited understanding of local structure around the tantalum ions, a problem that lies at the heart of predicting the micro- and macroscopic properties of these glasses. Herein, we present a novel approach for predicting the local structural environments in tantalum silicate glass based on a phase diagram approach. The phase relations and glass formation region of Li₂O–Ta₂O₅–SiO₂ ternary systems are explored to calculate the structure and additive physical properties of lithium tantalum silicate glasses. These measured and calculated results are in good quantitative agreement, indicating that the phase diagram approach can be applied broadly to Li₂O–Ta₂O₅–SiO₂ ternary glass systems. Using the phase diagram approach, the local structure of tantalum can be directly obtained. Each Ta atom is surrounded by six atoms, and its polyhedron, the TaO₆ octahedron, bonds through oxygen to Li and Ta. As a network modifier, Ta⁵⁺ depolymerizes the silicate glass structure by modulating the local structure of lithium atoms in Li₂O–Ta₂O₅–SiO₂ ternary glass system. The compositional dependence of structure in lithium tantalum silicate glasses is quantitatively determined based on the structure of the nearest neighbor congruent compound through the lever rule. These findings offer a precise prediction of tantalum silicate glass properties with quantitative control over local structural environment of the disordered materials.     

Glass Formation and Luminescence of Glasses in the Ga2S3–GeS2–Nd2S3System

The results of spectral measurements and the differential thermal analysis (DTA) data for glasses in the Ga₂S₃–GeS₂–Nd₂S₃system are presented. The boundaries of the glass formation region in the Ga₂S₃–GeS₂–Nd₂S₃system are determined. It is shown that the luminescence efficiency increases with an increase in the gallium sulfide content due to the displacement of the concentration quenching boundary of Nd³⁺luminescence with a change in the glass matrix composition.     

Crystallisation and characterisation of dielectric glass ceramics in Li2O–Al2O3–SiO2 system

Abstract

Glass ceramics in the Li₂O–Al₂O₃–SiO₂ system have been synthesised to produce bulk materials grown in a glass phase via quenching followed by controlled crystallisation. The crystallisation and microstructure of Li₂O–Al₂O₃–SiO₂ (LAS) glass–ceramic with nucleating agents (B₂O₃ and/or P₂O₅) are investigated by differential thermal analysis, X-ray diffraction and scanning electron microscopy and the effects of B₂O₃ and P₂O₅ on the crystallisation of LAS glass are also analysed. The introduction of both B₂O₃ and P₂O₅ promotes the crystallisation of LAS glass by decreasing the crystallisation temperature and adjusting the crystallisation kinetic parameters, allows a direct formation of β spodumene phase and as a result, increases the crystallinity of the LAS glass ceramic. Microstructural observations show that the randomly oriented, nanometre sized crystalline is found with residual glass concentrated at crystallite boundaries. Furthermore, it is interesting that codoping of B₂O₃ and P₂O₅ creates not much effect on the crystallisation temperature. The dielectric properties of the glass–ceramics formed through controlled crystallisation have a strong dependence on the phases that are developed during heat treatment. The dielectric constant is continuously increased and the dielectric loss is decreased with addition of additives where mobile alkali metal ions (e.g. Li⁺) are incorporated in a crystal phase and minimise the residual glass phase.     

Li2O-ZnO-SiO2微晶玻璃析晶动力学研究

利用经典Johnson-Mehl-Avrami(JMA)方程分析了含成核剂氧化钛的Li2O-ZnO-SiO2微晶玻璃的析晶动力学,并用XRD与SEM研究了热处理制度对玻璃析晶行为的影响.结果表明玻璃的晶化过程为多阶段晶化,在析晶初始阶段析出的晶体为γⅡ-LZS,当温度大于760℃时由在γⅡ-LZS的晶界开始生成方石英新相.采用Kissinger法计算得到γⅡ-LZS与方石英晶体的析晶活化能分别为315.2KJ/mol与343.7KJ/mol.