非水溶剂中纳米结构SrTiO3薄膜电极平带电位研究

本文制备了纳米结构SrTiO₃薄膜电极,并通过XRD、TEM和SEM对电极的结构和表面形貌进行表征。利用光谱电化学法,测定了纳米结构SrTiO₃电极在非水溶剂中的平带电位。研究发现:SrTiO₃电极在水中及非水质子溶剂(甲醇、乙醇)中的平带电位比在非水非质子溶剂(乙腈、四氢呋喃)中更正。在水及非水质子溶剂中,Li⁺的添加对 SrTiO₃电极的平带电位影响较小,而在非水非质子溶剂中,Li⁺的加入对 SrTiO₃电极的平带电位有较大影响,随着Li⁺浓度的增加,SrTiO₃电极的平带电位向电位更正的方向移动。     

Pb添加对MOD-YBCO超导膜结构和临界电流密度的影响

使用Pb添加方法改善钇钡铜氧(YBCO)超导膜的金属有机物沉积(MOD)制备中的形核和生长过程.通过引入一定量的三水合乙酸铅,配制出均一稳定的含Pb前驱溶液,经过涂覆和热处理制备YBCO超导膜,然后测量YBCO超导膜的微观结构和临界电流密度(Jc),从而研究了不同Pb添加量和不同水分压的影响.研究结果表明,当热处理期间的水分压较低(露点为25℃)时,Pb添加会使YBCO膜形成气孔,出现局域不致密的现象,从而导致Jc明显下降.当热处理期间的水分压较高(露点为45℃)时,使用Pb添加方法制备的YBCO膜致密程度提高,而且非c轴取向YBCO晶粒得到抑制,当Pb添加量为1.lwt;时YBCO超导膜的Jc最优,可达到3.7 MA/cm2(自场,77 K,370 nm厚).     

铌掺杂钛酸铋钠钾厚膜的制备及其铁电性能

根据粉末溶胶法的原理,用旋转涂覆工艺在Pt/Ti/SiO2/Si(100)衬底上制备不同Nb含量的(Na0.85K0.15)0.5 Bi0.5Ti(1-x)NbxO3(NKBTNx,x=0.01,0.03,0.05,0.07)厚膜,并研究了厚膜样品的微观结构、介电特性、漏导特性及铁电特性.XRD和SEM的分析结果表明:A位掺杂K、B位掺杂Nb并没有改变Na0.5 Bi0.5 TiO3的晶体结构;Nb的最佳掺入量为0.05.NKBTN5铁电厚膜具有最好的结晶度,尺寸均匀,厚膜表面光滑致密,但有少量微孔.介电频谱测试表明,NKBTNx厚膜的居里温度随着Nb含量的增加而逐渐增加,厚膜的弛豫特性明显增强.此外,NKBTN5铁电厚膜的室温介电常数最大,介电损耗最低,漏电流密度最小,剩余极化值最大(2Pr=48.1μC/cm2),矫顽场最小(77.8 kV/cm).     

In、Gd共掺对BaCeO3基质子导体性能的影响

高温质子导体利用质子传导可以被广泛地应用于燃料电池、氢分离膜和氢传感器等方面,因此受到广泛研究.本文采用柠檬酸盐法及改进的柠檬酸盐法制备了In、Gd共掺的BaCeO3基质子导体并对其微观形貌、化学稳定性和电导率进行了研究.结果表明,由于Gd的电负性较低,掺杂后提高了体系的碱性,导致其化学稳定性较差.但是,Gd的离子半径与Ce的离子半径相差很小,更利于离子传输,因此Gd单掺和In、Gd共掺的样品具有与传统质子导体相比拟的电导率.     

便携式电子设备用无铅压电扬声器的研制

用丝网印刷法在印有Pt电极的Al2O3基片上制备了BaTiO3(BT)掺杂Bi0.5(Na0.82K0.18)0.5 TiO3(BNKT)厚膜,研究了BT掺杂对BNKT厚膜相结构、微观形貌、介电、压电及铁电性能的影响.研究发现,(1-x)BNKT-xBaTiO3厚膜体系的准同型相界(MPB)位于3mol;相似文献   

溶胶电泳沉积法制备PZT压电厚膜及其性能研究

采用溶胶-凝胶方法制备Pb(Zr0.52Ti0.48)O3(PZT)纳米粉末,将此粉末按一定比例加入到同成分PZT溶胶中,采用溶胶-电泳沉积技术在ITO玻璃衬底上制备PZT厚膜.采用X射线衍射分析、SEM及HP4294A阻抗分析仪等对PZT膜进行了微观结构和介电性能测试,研究了电泳电压、热处理温度及电泳时间对PZT膜结构及膜厚的影响,结果表明,在1V电压下进行电泳,600℃热处理20min,可以得到表面均匀平整的纯钙钛矿结构PZT膜,以(110)择优取向,通过控制电泳时间可有效控制膜的厚度.获得了膜厚为30μm、介电常数达到ε33T/ε0=781、介电损耗为tanδ=0.0083、剩余极化与矫顽电场强度分别为24.6μC/cm2与61.9kV/cm铁电性能较好的PZT膜材料.     

DPPC与MMA混合单层LB膜缺陷结构的AFM研究

采用原子力显微镜(AFM)研究了转移到疏水石英基片上的二棕榈酰磷酯酰胆碱(DPPC)与不同浓度聚合物单体分子甲基丙烯酸甲酯(MMA)的混合物所形成的单层LB膜及其缺陷的微结构,研究了沉积压对缺陷的影响.当MMA的摩尔比为33;(即MMA∶DPPC＝1∶2),沉积压为5.0mN/m时,生成直径约3～4μm的圆形液态凝聚相(LC)畴区,LC畴区主要为DPPC与MMA的混合物,同时还分布着一些由聚合的MMA分子(即聚合物PMMA)形成的"小岛";当沉积压增加至15.0mN/m时,LC畴区中主要为聚合物PMMA的聚集体.当MMA的摩尔比增加至50;后,LC畴区中聚合物PMMA含量增加.畴区产生的主要原因是由于不同MMA含量和沉积压使DPPC和MMA及其聚合物PMMA产生不同程度的相分离所致.MMA/DPPC混合LB膜中这种圆形的畴区缺陷可以诱导形成圆形的一水草酸钙晶体沉积图形.     

静电纺丝法制备超疏水/超亲油SiO2微纳米纤维膜

采用静电纺丝法制备SiO2微纳米纤维膜,经六甲基硅氮烷(HMDS)改性后获得疏水/亲油特性,用FTIR、SEM、接触角等手段表征纤维膜的成分、微观形貌和对水及正十二烷的润湿性能等,研究了制备工艺对纤维膜物性参数以及润湿性能的影响,并测试了改性后纤维膜的高温稳定性和耐腐蚀性能.结果表明:SiO2微纳米纤维膜具有较多的孔隙和较高的比表面积,经HMDS改性后其表面粗糙结构结合疏水亲油的-Si(CH3)3基团使得纤维膜获得超疏水/超亲油特性,其水接触角为153.7°、水滚动接触角为8.2°、油接触角为0°;超疏水/超亲油SiO2微纳米纤维膜的最高耐受温度为450℃,最大拉伸强力为(40.7 ±9.4)×10-2N,且具有较好的耐腐蚀性能.     

低氟MOD法制备Zr掺杂YBCO厚膜的性能研究

提高膜厚是一种常用的提高YBCO涂层超导体导电能力的方法.如何在提高膜厚的基础上抑制薄膜的临界电流密度(Jc)在外场下的迅速下降是实现YBCO涂层导体产业化的关键.本文选用高钉扎效果的Zr掺杂YBCO复合薄膜进行膜厚和性能关系的研究,在LaAlO3基底上分别通过单次、两次、三次和四次涂覆制备了膜厚分别达200nm(单层膜)、400nm(双层膜)、600nm(三层膜)和800nm(四层膜)的Zr/YBCO复合薄膜,并详细研究了Zr/YBCO复合薄膜在不同膜厚下的微观结构、表面形貌以及超导性能.研究发现,低氟MOD法在重复涂覆制备厚膜的过程中大大节省了时间,提高了制备效率.此外,通过研究YBCO复合膜的厚度和临界电流的关系,得出如下结果:在厚度不超过600 nm的前提下,随着复合膜厚度的增大,其临界电流保持逐渐增加的趋势.其中,单层薄膜的上值最大,达到了3.34 MA/cm2;三层膜的Jc值达到了1.91 MA/cm2,其Ec值最大,达到了每厘米带宽114.6 A.     

气体流量及配比对CVD SiC膜层的影响

本文以甲基三氯硅烷(MTS)为先驱体原料,H2为载气,采用化学气相沉积工艺在反应烧结碳化硅表面制备SiC致密膜层。研究了不同反应气体流量及配比对CVD碳化硅膜层的影响。结果表明:反应气体的流量对膜层的表面形貌影响较大,较大的气流量容易使膜层剥落;减小反应气体流量有利于改善膜层的均匀性。H2/MTS比例影响沉积SiC膜层的相组成。当沉积温度为1200℃,H2/MTS比例为6∶1时,得到的膜层由SiC和C两相组成;当H2/MTS比例为12∶1时,膜层由SiC和Si两相组成;当H2/MTS比例为10∶1时,得到单一相的SiC膜层。在优化的工艺参数下,制备出致密的CVD膜层,经过光学加工后膜层的表面粗糙度为0.72 nm,平面度RMS为0.015λ(λ=0.6328μm)。     

Analysis of proton-conducting organic-inorganic hybrid materials based on sulphonated poly(ether ether ketone) and phosphotungstic acid via ASAXS and WAXS

In the present paper the distribution of phosphotungstic acid (PTA, H₃PW₁₂O₄₀) dispersed in sulfonated poly(ether ether ketone), SPEEK, was investigated by Anomalous Small Angle X-ray scattering (ASAXS) and Wide-Angle X-Ray Scattering WAXS techniques. The hydrolysis and condensation of 3-aminopropyltrimethoxysilane or zirconium tetrapropylate in this polymeric matrix were used to produce poly(3-aminopropyl silsesquioxane) or ZrO₂, as nanofillers. Contrary to previous results reported for membranes containing phosphomolybdic acid, the PTA could be completely dissolved in the SPEEK matrix. The applicability of the Guinier approximation for the SPEEK/PTA membrane confirmed that the PTA was dispersed as isolated nanoparticles. The incorporation of poly(3-aminopropyl silsesquioxane) in the SPEEK/PTA system caused the agglomeration of the heteropolyacid as 30 nm large particles. The ZrO₂ had little effect on the distribution of PTA in the SPEEK matrix. On the other hand, no crystallization of the heteropolyacid was observed in the membranes.     

TiO2 nanoparticles synthesis for application in proton exchange membranes

In the present paper, suitable TiO₂ nanoparticles are successfully synthesized by sol‐gel method, in order to utilize the freshly prepared TiO₂ nanoparticles for proton exchange membrane (PEM) preparation. Titanium tetrachloride (TiCl₄) is used as precursor and ethanol as a solvent. The optimum and suitable TiO₂ nanoparticles were obtained by varying gelatinisation time (4–120 h), concentration of precursor (TiCl₄) in ethanol (2–15 vol%), and reaction temperature (15–35 °C). The morphology, size and purity of the nanoparticles are investigated by transmission electron microscope (TEM), dynamic light scattering (DLS) and X‐ray diffraction (XRD). Optimum results were found at 4 h of gelatinisation time, 10% precursor concentration and 25 °C temperature for preparation of TiO₂ nanoparticles. Thus prepared nanoparticles are found to be suitable for preparation of nanocomposite PEM, and consequently the prepared PEM indicates enhanced properties, such as, higher thermal stability (high glass transition temperature of 184.1 °C), excellent proton conductivity (0.0822 S cm⁻¹ at room temperature) and low methanol permeability (1.11 × 10⁻⁹ cm2 s⁻¹).     

Preparation and the proton conductivity of chitosan/poly(vinyl phosphonic acid) complex polymer electrolytes

This study describes the preparation and proton conductivity of novel polymer complex electrolytes consisting of chitosan and poly(vinylphosphonic acid), PVPA. The materials were prepared via in situ polymerization of vinyl phosphonic acid in the presence of chitosan at various monomer feed ratios with respect to d-glucosamine repeat unit. Homogeneous materials were produced and they were extensively characterized for their compositions by elemental analysis (EA), thermal properties by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) and the morphology by X-ray diffraction (XRD). The complexation of chitosan/PVPA via proton exchange reactions was confirmed by Fourier transform infrared (FT-IR). The methanol permeability of CHPVPA₅ was lower than Nafion^® 115. The water/methanol uptake was measured and the results showed that solvent absorption of the materials increased with increasing PVPA content in the matrix. The temperature dependence of the proton conductivity of the complex electrolytes follows VTF behavior at higher x. Proton conductivity of CHPVPA₅ was measured to be approximately 3 × 10⁻⁵ S/cm at 120 °C in the anhydrous state.     

High porosity silica xerogels prepared by a particulate sol–gel route: pore structure and proton conductivity

The lower cost and higher hydrophilicity of silica xerogels could make them potential substitutes for perfluorosulfonic polymeric membranes in proton exchange membrane fuel cells (PEMFCs). For that purpose, we need to obtain micro or micro and mesoporous silica xerogels with a high porosity. The preparation of micro (<2 nm) and micro and mesoporous silica xerogels (2<d_poresize10 nm) from particulate as oppossed to polymeric suspensions of silica using tetraethyl orthosilicate (TEOS) as precursor is used. Two techniques of varying packing density have been performed in this work: (1) Control of the aggregation degree in the sol by adjusting its pH before gelation (pH 5, 6 and 8) and (2) Mixture of sols with a different average particle size (particles formed under acid and base catalyzed reactions). Proton conductivity of the obtained xerogels was studied as a function of temperature and relative humidity (RH). High pore volume, high porosity and small pore size SiO₂ xerogels have been achieved in the calcination temperature range from 250 to 550 °C. The calcined xerogels showed microporosity or micro and mesoporosity in the whole range of calcination temperatures. By mixing sols (molar ratio: acid/base=4.8) porosities up to 54.7±0.1% are achieved, at 250 °C of firing temperature. According to EMF measurements, electrical transport is due to protons in this kind of materials. The proton conductivity of the studied xerogels increased linear with measured temperature. A S-shaped dependence of the conductivity with the RH was observed with the greatest increase noted between 58% and 81% RH. Xerogels with a low porosity (40.8±0.1%) and an average pore size less than 2.0 nm showed lower values of proton conductivity than that of xerogels with a higher porosity and a higher average pore size in the whole range of temperature and RH. When silica xerogels, with the highest conductivity, are treated at pH 1.5, that property increased from 2.84×10⁻³±5.11×10⁻⁵ S/cm to 4.0×10⁻³±7.2×10⁻⁵ S/cm, at 81% RH and 80 °C. It indicates that the surface site density of these materials has a strong effect on conductivity. Proton conductivity values achieved are less than one order of magnitude lower than that of Nafion, under the same conditions of temperature and RH.     

Ce0.8Sm0.2O1.9-BaCe0.8Sm0.2O2.9复合电解质的成分对其电化学性能的影响

采用一步溶胶凝胶法制备摩尔比分别为9∶1、7∶3、5∶5和3∶7的复合电解质Ce0.8Sm0.2O1.9(SDC)-BaCe0.8Sm0.2O2.9(BCS)粉末,研究复合电解质SDC-BCS的相成分对电导率及其电化学性能的影响.结果表明:随着SDC含量的增加,复合电解质SDC-BCS的晶粒尺寸增大、电导率提高;复合电解质的晶界电导率均高于单相SDC的晶界电导率.不同成分的复合电解质制备的NiO-SDC-BCS|SDC-BCS|LSCF-SDC-BCS单电池的功率密度随着SDC含量的增加而提高.当SDC∶BCS的摩尔比为9∶1时,其单电池700 ℃的最大功率密度为550 mW/cm2,是单电池NiO-SDC|SDC|LSCF-SDC最大功率密度的3倍.     

Ce0.8Sm0.2O2-δ-Ca3Co2O6-δ双相材料的制备及其透氧性能研究

采用共沉淀法和柠檬酸络合法分别制备了Ce0.8Sm0.2O2-δ和Ca3Co2O6-δ粉体,随后通过固相烧结法获得了致密Ce0.8Sm0.2O2-δ-Ca3Co2O6-δ双相透氧膜材料.分别通过X射线衍射(XRD)和场发射扫描电子显微镜(FESEM)对样品的晶体结构和形貌进行了表征.系统研究了双相比例对样品的热膨胀系数、电子电导率和透氧率的影响.实验结果表明该双相材料具有优异的化学稳定性,1150 ℃烧结6 h可以获得致密双相膜.双相膜具有较低的热膨胀系数,为13.47×10-6 ~14.23×10-6 K-1,接近电解质的热膨胀系数值.当离子导电相添加量由40wt;增加到80wt;,双相膜的电导率随之降低,而透氧率随之增大,950 ℃时,质量比为8∶2的Ce0.8Sm0.2O2-δ-Ca3Co2O6-δ双相膜的透氧率达到了2.80×10-7 mol·cm-2·s-1,表明该材料可以作为一种新型双相透氧膜材料用于氧分离.     

HNTs/SiO2复合气凝胶制备及其性能研究

采用正硅酸乙酯(TEOS)为硅原,以硅烷改性的埃洛石纳米管(HNTs)为增强相,利用CO2超临界干燥技术制备具有优良力学和隔热性能的HNTs/SiO2复合气凝胶.利用傅立叶红外光谱、扫描电镜、比表面积与孔径分析仪、万能试验机和导热率测量仪等手段对HNTs改性后的表面状态、HNTs/SiO2复合气凝胶的微观形貌、孔结构、力学和导热性能进行了测试分析.结果表明:改性后的HNTs均匀分散到二氧化硅气凝胶基体中,并与SiO2纳米颗粒实现良好的结合,HNTs/SiO2复合气凝胶呈三维网络结构,当HNTs含量为15wt;时,平均孔径为10.47 nm;随着HNTs含量的增加,复合气凝胶的力学性能不断增强,同时其导热系数也不断增大,当HNTs含量为15wt;时,HNTs/SiO2复合气凝胶的抗压强度为0.85 MPa,导热系数为0.024 W/mK.     

Influence of TiO2 on proton conductivity in fuel cell electrolytes based on sol–gel derived P2O5–SiO2 glasses

P₂O₅–TiO₂–SiO₂ based glasses have been prepared by a sol–gel process. The glasses were characterized by structural, thermal, nitrogen adsorption–desorption and conductivity measurements. The structural formation has been confirmed by the FTIR and NMR analysis. The proton conductivity of the glasses increased linearly with increase in temperature. Glasses with an average pore size less than 2 nm showed higher values of proton conductivity in humid atmosphere. The conductivity value increased from 6.47 × 10⁻⁴ S/cm to 3.04 × 10⁻² S/cm at 70% RH in the temperature range 30–90 °C. We observed in fuel cell measurements that the performance of the E1 electrode is superior to that of the other electrodes at the same operating condition. The power density shows a similar pattern to current density.     

Flexible and high ion conducting solid polymer electrolytes prepared via ring-opening polymerization

Abstract

The chemical cross-linking of epoxy resin has been known as an imperative way to improve the mechanical strength and thermal stability of solid polymer electrolytes (SPEs). Herein, we prepare flexible epoxy-based SPEs with high ion conductivity for electrochemical devices via ring-opening polymerization. A diglycidyl ether of bisphenol-A (DGEBA) epoxy resin was selected as the mechanical supporting SPE matrix. The high flexibility of SPEs can be obtained by adding poly(ethylene glycol) diglycidyl ether (PEGDE) plasticizer to the epoxy resin. Furthermore, the incorporation of electrolyte mixture of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salts and 1-butyl-3 methylimidazolium bis(trifluorosulfonyl)imide (BMIM-TFSI) ionic liquids allows for boosting ionic conductivity of the epoxy-based SPEs. Consequently, the high room temperature ionic conductivity ～2.4?×?10^?3 S/cm was achieved in the SPE containing 30?wt% of the epoxy and 70?wt% of the electrolyte mixture.     

Protonic conduction in alkaline earth metaphosphate glasses containing water

D.c. electrical conductivity data were obtained for M O·P₂O₅ glasses (M = Be, Mg, Ca, Sr, Ba) containing small amounts of water. The results suggest that the mobility of protons in the glasses increases with decreasing OH bonding strength. The relation between the proton concentration and the conductivity or the apparent activation energy was studied for calcium metaphosphate glasses containing various amounts of water. The conductivity was found to be proportional to the square of the proton concentration; the apparent activation energy decreased linearly with increasing logarithm of proton concentration.