Characterization of the negative thermal expansion material Zr_(1-x)Hf_xW_2O_8

The oxide ZrW_2O_8 displays unusual property of isotropic negative thermalexpansion in a large wide temperature range, which makes it have a number of important potentialapplications. The cubic Zr_(1-x)Hf_xW_2O_8 (x velence 0,0.3, 0.5, 0.7, and 1.0) were synthesized bystandard solid state reaction technique. The high and low temperature X-ray diffraction analysisindicate that the substitution of the Hf^(4+) for Zr^(4+) only leads to reducing the latticeconstants, and the changes of negative thermal expansion coefficients are not obvious. The linearexpansion coefficients of Zr_(1-x)Hf_xW_2O_8 (x velence 0,0.3, 0.5, 0.7, and 1.0) are about -6 X 10^(-6) K^(-1) in the temperature range of 298 to 973 K, while that of Zr_(0.5)Hf_(0.5)W_2O_8 is -9.6X 10^(-6) K_(-1) from 83 to 298 K. The phase transition temperatures from alpha-ZrW_2O_8 tobeta-ZrW_2O_8 structure were also determined by X-ray diffraction method. Thermogravimetric analysis(TGA) exhibits that Zr_(1-x)Hf_xW_2O_8 is not hygroscopic in air.

NASICON型Na_(1+x)Zr_(2)Si_(x)P_(3-x)O_(12)固态电解质及其钠金属电池研究进展

锂离子电池由于具有较高的工作电压和能量密度实现了商业化。然而,有限的锂资源限制了其广泛应用。钠离子电池展现出与锂离子电池相似的电化学特性,并且钠盐资源更加丰富,因此受到了广泛关注。目前,钠离子电池使用的是有机电解液,这存在一系列安全隐患,如漏液和燃烧等,采用固态电解质可以有效解决这些问题。然而,电解质的离子电导率仍有待提升,且材料制备的一致性及与电极间的界面阻抗问题限制了其广泛应用。针对离子电导率的问题,总结分析了不同价态离子取代的影响。针对存在的界面问题,从正极、负极两侧分析了现有Na_(1+x)Zr_(2)Si_(x)P_(3-x)O_(12)电解质的界面改性方法。最后,对Na_(1+x)Zr_(2)Si_(x)P_(3-x)O_(12)电解质的发展方向进行了展望,有望推动固态钠离子电池的发展。

PEG-2000添加量对Pr_(x)Zr_(1-x)O_(2-δ)催化氧化NO活性的影响

采用溶胶-凝胶法制备了Pr_(x)Zr_(1-x)O_(2-δ)催化剂,并用于NO催化氧化。以聚乙二醇-2000(PEG-2000)为模板剂对催化剂进行改性,研究了不同模板剂添加质量分数对NO催化氧化活性的影响。结果表明,催化剂活性随PEG-2000添加质量分数的增加而降低;在300℃、PEG-2000添加质量分数为2%时,Pr_(x)Zr_(1-x)O_(2-δ)的催化活性最高,NO转化率达到了94.81%。利用XRD、SEM、N2吸附-脱附、XPS及FT-IR对催化剂进行表征,结果表明,模板剂添加质量分数的变化不会改变催化剂Pr_(2)Zr_(2)O_(7)晶型;催化剂为介孔结构,质量分数为2%时的比表面积和孔容最大,有利于催化氧化NO。此外,模板剂质量分数的增加会增强催化剂的亲水性。

Ce_(x)Zr_(1-x)O_(2)储氧材料制备方法研究进展

本文综述了共沉淀法、溶胶-凝胶法、水热法、高能球磨法等常用Ce_(x)Zr_(1-x)O_(2)储氧材料的合成方法,并进行了比较。阐述了Ce_(x)Zr_(1-x)O_(2)的基本改性机制,详述了稀土元素、碱土元素以及过渡金属对Ce_(x)Zr_(1-x)O_(2)的改性效果及原理。相关研究结果表明,Ce_(x)Zr_(1-x)O_(2)晶体结构、形貌、比表面积与其合成方法有很大关系,从而影响其储氧性能和热稳定性。通过掺杂第三种元素与Ce_(x)Zr_(1-x)O_(2)形成三元固溶体能进一步改善其储氧性能和热稳定性,从而使CO和HC在还原条件下以及NO_(x)在氧化条件下的转化率大大提高。最后,本文指出了Ce_(x)Zr_(1-x)O_(2)储氧材料目前存在的问题和今后的研究方向。

微波焙烧对纳米Ce_(x)Zr_(1-x)O_(2)固溶体微观结构及其NH_(3)-SCR催化性能的影响

采用微波加热将通过水热法合成的Ce_(x)Zr_(1-x)O_(2)(0<x≤1)固溶体前驱体在500℃进行焙烧2 h,最终得到不同配比的纳米Ce_(x)Zr_(1-x)O_(2)固溶体粉末状样品.研究不同配比的Ce_(x)Zr_(1-x)O_(2)的结构和微观形貌对其NH_(3)-SCR催化性能的影响.结果表明,利用微波炉合成的Ce_(x)Zr_(1-x)O_(2)固体粉末中,当CeO_(2)中掺入Zr元素形成Ce_(0.4)Zr_(0.6)O_(2)固溶体之后,Ce_(0.4)Zr_(0.6)O_(2)比表面积比CeO_(2)增加了1倍,NH_(3)-SCR最高脱硝活性也由42.4%增加到90.0%.当n Ce∶n Zr=4∶6时,其微观形貌最好,颗粒的分散度较高,同时,其NH_(3)-SCR脱硝活性达到Ce_(x)Zr_(1-x)O_(2)中的最大值90.0%.

Pr/Zr原子比对Pr_(x)Zr_(1−x)O_(2−δ)催化氧化脱硝活性的影响

采用溶胶-凝胶法制备了不同Pr/Zr原子比的Pr_(x)Zr_(1−x)O_(2−δ)催化剂用于催化氧化脱硝。结果表明,催化氧化脱硝效率随Pr原子比的增加而先提高后降低;当Pr/Zr原子比为5∶5时,在250°C下,最佳脱硝活性可达94.62%。采用SEM、N_(2)吸附-脱附、XRD、XPS、H_(2)-TPR和FT-IR对催化剂进行了表征。结果表明,活性最好的催化剂(Pr_(0.5)Zr_(0.5)O_(2−δ))具有“层状”形貌,表面孔隙多,比表面积大,孔体积分别为77.74 m^(2)/g和0.66 cm^(3)/g。此外,随着Pr原子的增加,晶相从c-ZrO_(2)转变为Pr_(2)Zr_(2)O_(7)。XPS和H_(2)-TPR结果表明,表面化学吸附氧和表面Pr^(4+)氧化物增加,Pr原子比的上升有利于产生氧空位(Vӧ),有利于提高催化氧化脱硝效率。FT-IR表征结果表明,Pr_(0.5)Zr_(0.5)O_(2−δ)固溶体具有较高的NO选择性,有利于NO的催化氧化。抗SO_(2)和H_(2)O毒性实验表明,5∶5的Pr/Zr原子比的催化剂具有更好的抗毒性。此外,利用IC分析吸收产物,结果表明,吸收液中的主要产物是NO_(2)^(-)和NO_(3)^(-)。

Effects of Er^(3+)doping on structure and thermal properties of(Sm_(1-x)Er_(x))_(2)Zr_(2)O_(7)ceramics for thermal barrier coating

Rare earth Er^(3+)doped(Sm_(1-x)Er_(x))_(2)Zr_(2)O_(7)(x=0.1,0.2,and 0.3)ceramic samples were synthesized using a solid state reaction method.The microstructure and thermal properties of these ceramics were investigated to evaluate their potential as thermal barrier coating materials.The results show that ceramics are compact with regular-shaped grains of 1-5μm size.(Sm_(1-x)Er_(x))_(2)Zr_(2)O_(7)has a pyrochlore structure mainly determined by ionic radius ratio,but the ordering degree decreases with increase of the Er_(2)O_(3)content.There is no phase transformation from 1000 to 1200℃,and the(Sm_(1-x)Er_(x))_(2)Zr_(2)O_(7)ceramics exhibit excellent phase stability during thermal treatment at 1200℃for 100 h and 1400℃for 50 h.The thermal conductivities of dense(Sm_(1-x)Er_(x))_(2)Zr_(2)O_(7)ceramics range from 1.52 to 1.59 W/(m·K),which is lower than that of Sm_(2)Zr_(2)O_(7),and decrease as the Er2O3content increases.Besides,the thermal expansion coefficient of(Sm_(1-x)Er_(x))_(2)Zr_(2)O_(7)is higher than that of Sm_(2)Zr_(2)O_(7).

陶瓷-聚合物复合固态电解质膜的制备与性能研究

NASICON型快离子导体Li_(1+x)Al_(x)Ti_(2-x)(PO_(4))_(3)(LATP)具有较高的离子电导率、较宽的电化学窗口及良好的水和空气稳定性,但其界面接触性能差。石榴石型Li_(7)La_(3)Zr_(2)O_(12)(LLZO)锂离子电导率高、电化学窗口较宽且热稳定性好,但其立方相结构不稳定,影响其实际应用。采用溶液浇筑法,制备纯PVDF-LiTFSI电解质膜和以PVDF为基、3种不同质量比的Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)和Li_(1+x)Al_(x)Ti_(2-x)(PO_(4))_(3)的固态电解质膜,并探讨纯PVDF-LiTFSI电解质膜和3种不同质量比的活性无机电解质填料对复合固态电解质离子电导率的影响。结果表明,Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)和Li_(1+x)Al_(x)Ti_(2-x)(PO_(4))_(3)质量比为1∶1时,电解质膜的XRD图谱的衍射峰比纯PVDF-LiTFSI下降更为明显,电化学窗口为3.9 V左右,表现出更好的稳定性。在不同温度下分别测量其离子电导率发现,Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)和Li_(1+x)Al_(x)Ti_(2-x)(PO_(4))_(3)质量比为1∶1时的电解质膜均高于纯PVDF-LiTFSI电解质膜和Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)和Li_(1+x)Al_(x)Ti_(2-x)(PO_(4))_(3)质量比为2∶1和3∶1时的电解质膜。将其装配成电池后发现,0.1C下电池首次充放电比容量分别为90 m A·h/g和87 m A·h/g。以0.5C的电流循环25圈,放电比容量从57 mA·h/g衰减至51mA·h/g,容量保持率为99.7%。所以,以PVDF为基、Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)和Li_(1+x)Al_(x)Ti_(2-x)(PO_(4))_(3)质量比为1∶1的固态电解质膜有优良的倍率性能和循环稳定性能。

高性能铪锆氧铁电材料与器件先进调控技术研究进展

重点阐述和总结了近年来面向高性能氧化铪基铁电材料和器件的先进调控技术,包括应力调控、氧空位调控、界面微结构调控以及尺寸调控等。通过电极材料对铁电薄膜施加拉伸应力以提高其铁电性能,应力工程为先进2D/3D结构铁电存储器(FRAM)开发提供了重要的技术手段;氧空位的存在降低了铁电相与稳定相之间的能量差从而稳定铁电相;界面微结构调控有效减少界面副反应和缺陷;尺寸调控可以限制晶粒大小、改善均匀性。这些调控技术不仅能显著提高单一铁电器件的稳定性和可靠性,还将在改善铁电存储阵列均匀性、铁电多值存储特性等方面发挥重要的作用。