Enhancement of the ionic conductivity of poly(ethylene oxide) electrolyte film by polyaniline addition

To improve the electrical conductivity of LiClO₄–poly(ethylene oxide) (PEO) complex, nonconductive polyaniline (NPANI) was employed as an additive. The electrical conductivity of the PEO–LiClO₄–NPANI electrolyte was at least ten times that of the original PEO–LiClO₄ electrolyte. The amine and/or imine nitrogen atoms in the NPANI polymer chain as well as the oxygen atoms in the PEO poly-merchain attracted the Li⁺ ions, and ion-dipole interaction occurred. The interaction enhanced the mobility of the ClO₄ ^– ions. The positively charged nitrogens were electronically stabilized in the entire polymer chain because NPANI had conjugated electrons. The mechanism is unique and different from those of other polymer additives. It is the very first example in which NPANI was employed as the additive for the PEO solid electrolyte and in which NPANI was found to be an effective additive. In addition, the NPANI addition hardly affected the physical properties of the PEO matrix such as the glass transition temperature and the melting temperature.     

PAN–PEO solid polymer electrolytes with high ionic conductivity

The transparent and flexible solid polymer electrolytes (SPEs) are fabricated from polyacrylonitrile–polyethylene oxide (PAN–PEO) copolymer. The formation of the copolymer is confirmed by Fourier-transform infrared spectroscopy (FTIR) and Gel permeation chromatography (GPC) measurements. The effects of acrylonitrile (AN) wt% content and M_n(PEO) on ionic conductivity are investigated by alternating current (ac) impedance spectroscopy. By controlling and adjusting the AN wt% content and doping PEO with high molecular weight, the ionic conductivity of SPEs is optimized. The ionic conductivity of PAN–PEO solid polymer electrolytes is found to be high 6.79 × 10⁻⁴ S cm⁻¹ at 25 °C with an [EO]/[Li] ratio of about 10, and are electrochemically stable up to about 4.8 V versus Li/Li⁺. The conductivity and interfacial resistance remain almost constant even at 80 °C.     

PEO基固态聚合物电解质膜的静电纺丝制备及性能EI北大核心CSCD

PEO基固态聚合物电解质被认为是目前固态锂电池领域极具产业化前景的固态电解质。为适应工业化生产,采用静电纺丝技术制备PEO/LiClO_(4)固态聚合物电解质(SPE),研究纺丝电压、纺丝液质量浓度和锂盐含量对SPE纤维膜形貌和直径的影响。通过扫描电子显微镜观察SPE中纤维的形貌,利用Image J软件分析SPE纤维的直径。通过DSC,XRD,FTIR-ATR和拉伸测试等手段对静电纺丝制备的SPE纤维膜的组成、结构、性能等进行研究。结果表明:当纺丝电压为15 kV、PEO/LiClO_(4)纺丝液质量浓度为6%、[EO]∶[Li^(+)]=10∶1(摩尔比)时,静电纺丝方法制备的PEO/LiClO_(4) SPE纤维膜具有较好的纤维形貌,平均直径为557 nm,分布均一;当[EO]∶[Li^(+)]=10∶1时,SPE纤维膜中PEO的熔点仅为53.8℃,结晶度低至18.9%;电解质在30℃时的离子电导率达到5.16×10^(-5)S·cm^(-1),同时具备良好的电化学稳定性和界面稳定性。     

无定型PEO聚合物的合成及导电性能研究

利用低分子量PEG(Mn=400)合成了高分子量的聚氧化乙烯(PEO)嵌段聚合物。采用电化学方法——电渗析除尽了经常规方法(吸附、过滤、沉淀等)所不能除尽的微量杂质,得到纯化产物。通过GPC测得其平均分子量可达105。XRD和1HNMR表明其结构是以[CH2O(CH2CH2O)n]为重复单元的无定型聚合物,其与LiClO4络合物通过10％SiO2纳米材料补强后的固态电解质成膜性和导电性均良好。在测量温度范围内,电导率随温度的变化遵循Arrhenius关系式,22℃时Li+电导率达3.27×10-5 S/cm。     

先驱体转化法制备SiCO陶瓷粉体的氧化性能

以先驱体转化法制备的SiCO陶瓷粉体为原材料,采用热重法研究了粉体在干燥空气中的氧化性能。采用液态聚碳硅烷裂解制备的SiCO 陶瓷粉体平均粒径为7μm,氧化处理温度分别为：900℃、950℃、1000℃、1050℃,氧化时间均为4 h。结果表明：液态聚碳硅烷裂解制备的SiC_{1. 12}O_{0. 12}陶瓷粉体在1173～1373 K、干燥空气中,氧化增重表现为典型的2阶段变化规律：900℃ 下的前80 min至1050℃下的前20 min时间内,材料氧化表现为快速增重趋势;随后较长的氧化时间里,材料内部气孔的氧化由于封孔而停止,氧化反应主要由扩散控制,样品增重不太明显。经计算SiCO陶瓷粉体的氧化活化能为121 kJ/mol,并在此基础上推导了热重法与厚度测量法获得的2种氧化速率常数的转变公式。     

水铝英石/PEO/LiClO4复合固态聚合物电解质中组分相互作用对PEO结晶的影响

为解决现有锂离子电池的安全性问题,固态电解质的研究备受关注。以Na2SiO3和AlCl3·6H2O为原料,采用溶胶-凝胶法制备出水铝英石(AL);通过溶液共混法将其与聚环氧乙烷/高氯酸锂(PEO/LiClO4)复合得到复合固态聚合物电解质。利用X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)、差示扫描量热分析仪(DSC)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)以及光学显微镜(OM)对样品进行结构分析及形貌表征。结果表明:水铝英石和LiClO4与PEO间的非价键力相互作用(络合、氢键及Lewis酸-碱作用)显著抑制PEO的结晶。随着水铝英石含量的增加,PEO的结晶度呈现出先降低后增加的趋势;而随着锂盐含量的增加,PEO的结晶度持续降低,当EO/Li+摩尔比为10∶1,水铝英石的含量为5%(质量分数)时,复合固态聚合物电解质的结晶度最低,仅为4.12%。     

Effect of complexing salt on conductivity of PVC/PEO polymer blend electrolytes

Solid polymer electrolyte membrane comprising poly(vinyl chloride) (PVC), poly(ehylene oxide) (PEO) and different lithium salts (LiClO₄, LiBF₄ and LiCF₃SO₃) were prepared by the solution casting technique. The effect of complexing salt on the ionic conductivity of the PVC/PEO host polymer is discussed. Solid polymer electrolyte films were characterized by X-ray diffraction, FTIR spectroscopy, TG/DTA and ac impedance spectroscopic studies. The conductivity studies of these solid polymer electrolyte (SPE) films are carried out as a function of frequency at various temperatures ranging from 302 K to 353 K. The maximum room temperature ionic conductivity is found to be 0·079 × 10^?4 S cm^?1 for the film containing LiBF₄ as the complexing salt. The temperature dependence of the conductivity of polymer electrolyte films seems to obey the Vogel-Tamman-Fulcher (VTF) relation.     

Morphology and ionic conductivity of solid polymer electrolytes based on polyurethanes with various topological structures

Polyurethanes with linear, hyperbranched and comb-crosslinked structures were synthesized and were used to prepare solid polymer electrolytes. The polymer electrolytes were characterized by means of Fourier transform Raman spectroscopy, impedance spectroscopy (IS) and atomic force microscopy (AFM). The results showed that salt concentration significantly influences the morphology and conductivity of the three kinds of polyurethane/LiClO₄ system. When the mole ratios of the ether oxygen atom to lithium ion were controlled to be 12, 4 and 4 respectively for linear, hyperbranched and comb cross-linking polyurethane, the electrolytes typically displayed micro-phase separated morphology and the ionic conductivity also reached maxima respectively at 2.2 × 10^–7 S/cm, 2.8 × 10^–6 S/cm and 2.8 × 10^–5 S/cm at room temperature.     

Thermal conductivity of ceramic particle filled polymer composites and theoretical predictions

Models and theories for predicting the thermal conductivity of polymer composites were discussed. Effective Medium Theory (EMT), Agari model and Nielsen model respectively are introduced and are applied as predictions for the thermal conductivity of ceramic particle filled polymer composites. Thermal conductivity of experimentally prepared Si₃N₄/epoxy composite and some data cited from the literature are discussed using the above theories. Feasibility of the three methods as a prediction in the whole volume fraction region of the filler from 0 to 1 was evaluated for a comparison. As a conclusion: both EMT and Nielsen model can give a well prediction for the thermal conductivity at a low volume fraction of the filler; Agari model give a better prediction in the whole range, but with larger error percentage.     

Influence of sputtering pressure on the structure and ionic conductivity of thin film amorphous electrolyte

Ionic conducting thin film amorphous electrolytes are promising candidates for microelectronics applications. This study presents an investigation into the structure and composition of lithium phosphorus oxynitride (LiPON) thin film electrolyte prepared using radio frequency (RF) sputtering on Li₃PO₄ target. The ionic conductivity of LiPON thin films has been dramatically improved by decreasing N₂ pressure. X-ray photoelectron spectra (XPS) were used to determine the structure and composition of LiPON thin films. It was found that increasing the N₂ pressure during the deposition process resulted in a greatly decreased formation of triply coordinated –N<(N_t) as compared to doubly coordinated –N=(N_d) in LiPON thin films. These results indicate that the N_t structural unit plays an important role in the improvement of ionic conductivity as compared to the N_d structural unit. It also shows that PO₂N₂ tetrahedra with two N_t structural units exist in LiPON thin films at low N₂ pressures. Consequently, the improved ionic conductivity of the LiPON thin film deposited at low pressure results from the existence of PO₂N₂ tetrahedra with two N_t structural units in LiPON thin film. PO₂N₂ tetrahedra with two N_t structural units provides higher cross-linking density of the glass network and lower electrostatic energy than with two N_d structural units.     

Synthesis of TiO2 and TiN nanosize powders by intense light ion-beam evaporation

Ultrafine nanosized powders of TiO2 and TiN have been synthesized by the reactive ion-beam evaporation technique. In an oxygen or nitrogen atmosphere (1–10 Torr), a high-power-density ion beam (about 0.4 GW cm-2) is focused onto a Ti target; as a result of the interaction between ablated particles and gas, fine and ultrafine powders are synthesized. The influence of gas pressure and target–collector distance on the particle composition, size distribution and shape have been studied. At longer target–collector distances and higher pressures, powders in the 4–45 nm range are collected while, at shorter distances and lower pressures, the powders are in the micrometre range. TiO2 particles are spherical in shape, while TiN particles are cubic.     

Preparation and study of conductivity in lithium salt complexes of mixed MEEP : PEO polymer electrolytes

Poly(ethylene oxide)-LiX complexes and poly[bis(methoxy ethoxy ethoxide) phosphazene]-LiX complexes of polymer thin films were prepared. Conductivity measurements were carried out and the values were found to lie between 10⁻⁸ and 1.7 × 10⁻⁵ (S/cm). MEEP : LiX salts showed higher conductivity than PEO-LiX salts despite lower dimensional stability. For enhancing stability and conductivity, MEEP-PEO : (LiX) _n systems were prepared and conductivity measurements carried out. Further the MEEP/PEO : (LiX) _n was doped with Al₂O₃ and TiO₂ nanocomposite ceramic fillers and the conductivity was studied. The conductivity vs temperature plots showed the enhancement of conductivity with TiO₂ added nanocomposite ceramic fillers. The enhanced conductivity is explained on the basis of the effect of local structural modification—promoting localized amorphous region—for enhancement of the Li⁺ ion transport.     

Effects of Al2O3 addition on the sinterability and ionic conductivity of nasicon

The effects Al₂O₃ doping on the sintering behaviour and ionic conductivity of nasicon have been investigated using formulations of Na_3+2x Zr₂Si₂Al _x P_1–x O₁₂ where Al³⁺ ions were substituted to P⁵⁺ sites within the range 0x0.2. The density of Na_3+2x Zr₂Si₂Al _x P_1–x O₁₂ was increased with increasing amount of Al₂O₃ doping due to the enhanced liquid-phase sintering. The relative density of Na_3.4Zr₂Si₂Al_0.2P_0.8O₁₂ reached a maximum value of 96% when sintered at 1200°C for more than 7 h. The maximum conductivity of 0.24 ^–1 cm^–1 at 300°C was obtained for the composition with x=0.1 when sintered at 1200°C for 10 h.     

Enhancement of electrical conductivity and emission stability of oxide cathodes using Ni addition

An investigation has been carried out into the use of conductive phase additions to enhance the conductivity and emission behavior of the oxide cathode coating as used in CRTs. Electrical and emission characteristics have been studied for various additions of filamentary nickel (Ni) added to the sprayed strontium-barium carbonate precursors prior to spray deposition, followed by conventional thermal conversion and activation processes in vacuum. The conductivity and the electronic activation energy have been studied as a function of temperature in the range 300 to 1250 K, during conversion and activation processes allowing the conduction behavior to be compared to conventional materials. The conduction behavior has been found to change as a function of heat-treatment temperature as the conduction paths develop and subsequently evolve in the microstructure of the resultant composite coating during conversion, activation and subsequent aging/service life conditions, with metallic-dominated conduction at temperatures below 850 K and pore conduction mechanisms dominating at higher temperatures. The emission characteristics immediately after conversion are impaired by the Ni addition, however, the long-term emission characteristics show improvement with the conductive phase.     

Sinterability of commercial 8 mol% yttria-stabilized zirconia powders and the effect of sintered density on the ionic conductivity

The sintering behaviour of a number of commercially produced 8 mol% yttria-stabilized zirconia powders has been studied. The effect of different sintering regimes on the density and microstructure of the sintered ceramic was determined using density measurements, scanning electron microscopy (SEM) and dilatometry. The chemical homogeneity, particle size and the morphology of the as-received powder were related to the sintering behaviour of the different commercial powders. Powders prepared via a route which involved a spray-drying step sintered more readily than those prepared without a spray-drying step. Plasma-derived powders did not sinter to as high an apparent density as co-precipitated powders. The effect of sample density on the ionic conductivity of sintered YSZ ceramics was studied using a.c. impedance spectroscopy. This technique allowed separation of the bulk and grain-boundary components, enabling clear intepretation of the effects of sample porosity of the conduction pathways. Ceramics prepared from the three different powders achieved a bulk ionic conductivity of 16 S cm-1 at 1000 °C for sintered densities of 95% or greater. The results obtained are compared to values reported for a variety of other commercial powders. © 1998 Kluwer Academic Publishers