静电纺丝法制备La0.67Ba0.33MnO3微纳米纤维及其红外发射率研究

采用静电纺丝法结合溶胶-凝胶技术制备了钙钛矿型La_0.67Ba_0.33MnO₃微纳米纤维, 并利用差示扫描量热-热失重分析(DSC-TGA)、 X射线衍射(XRD)、 傅里叶变换红外光谱(FTIR)和扫描电子显微镜(SEM)等技术对产物进行了表征, 利用IR-2红外发射率测试仪测试了La_0.67Ba_0.33MnO₃在280~370 K范围内的红外发射率. 结果表明, La_0.67Ba_0.33MnO₃在600 ℃时已形成钙钛矿结构. 随着煅烧温度的升高, La_0.67Ba_0.33MnO₃的形貌由纤维状向三维网络状转变, 并最终失去纤维形态. 在280~370 K范围内, La_0.67Ba_0.33MnO₃微纳米纤维的红外发射率随温度升高而升高, 由0.564增加至0.689. 利用钙钛矿材料双交换理论解释了这一现象, 并进一步探讨了其在红外发射率可变材料中的应用前景.     

熔融碱法制备三重价态钙钛矿锰氧化物

以MnO₂, Ca(OH)₂和La(OH)₃为反应原料, 在惰性气氛、 低温(500 ℃)熔融KOH体系中合成了具有菱形钙钛矿结构Ca, K共掺杂的La_0.64Ca_0.25K_0.11MnO₃纳米材料, 并对Mn的价态及磁学性能等进行了讨论. X射线光电子能谱(XPS)分析结果表明, La_0.64Ca_0.25K_0.11MnO₃纳米材料中的Mn具有三重混合价态, 其零场冷却低温磁化率曲线表现出顺磁-铁磁转变, 居里温度(T_c)为280 K.     

多孔钙钛矿型氧还原催化剂在柔性铝空气电池中的应用研究

钙钛矿型催化材料作为贵金属的低成本替代物受到广泛关注,其用作氧还原反应催化剂具有非常可观活性和稳定性.目前相关工作主要集中在使用钙钛矿制备技术影响元素组成、形态、表面积和结构控制等方面.对于普遍存在的钙钛矿（ABO₃）材料而言,制备过程煅烧温度较高导致合成材料比表面积通常较小,限制了其在非均相催化反应中活性的提升.本文借助无机模板SiO₂制备具有高活性的大比表面的钙钛矿型催化材料La_0.7Sr_0.3MnO₃（LSMO）.测试结果表明,模板法LSMO具有非常可观的比表面积（31.1825 m²·g^-1）,用在柔性铝空气电池中放电电压相比于无模板法和溶胶凝胶法可分别提高8.2%和24.5%,且在大电流放电下性能衰退明显减缓.在电池变形状态下,输出电压可稳定在1.38 V以上.不仅为燃料电池商业化提供了解决方案,同时为未来可变性电源发展提供了新方向.     

负载型钙钛矿La0.8Sr0.2MnO3/SBA-15催化燃烧甲苯的研究

采用逐层负载-孔道内氨/水蒸气原位羟化法制备了一系列负载型钙钛矿La_0.8Sr_0.2MnO₃/SBA-15催化剂,用XRD、BET、TG-DTG、XPS、H₂-TPR等手段对催化剂的物性结构等进行了表征,并在常压连续流动固定床反应器上评价了该催化剂对甲苯催化燃烧的催化性能。结果表明,逐层负载-孔道内氨/水蒸气原位羟化法的使用有助于活性组分La_0.8Sr_0.2MnO₃进入SBA-15的孔道,并在SBA-15上形成钙钛矿结构。La_0.8Sr_0.2MnO₃/SBA-15上钙钛矿结构的形成和晶格氧的出现,可为催化剂提供较多的活性中心,有利于其催化燃烧甲苯的活性。     

铥掺杂钙钛矿锰氧化物La0.7Sr0.3MnO3的临界行为和磁熵变研究

在钙钛矿锰氧化物La_0.7Sr_0.3MnO₃的La位掺杂Tm³⁺,研究掺杂对体系结构、磁性、磁相变附近的临界行为和磁熵变的影响。通过掺杂调节A位平均离子半径,使体系居里温度更趋近室温;利用Kouvel-Fisher方法分析磁转变温度附近的临界行为,La_0.7Sr_0.3MnO₃的临界指数与三维海森堡模型的临界指数非常接近,表明未掺杂时磁相变附近的铁磁耦合为短程有序。掺杂Tm³⁺后样品La_0.65Tm_0.05Sr_0.3MnO₃的铁磁临界指数β趋近于海森堡模型,但顺磁临界指数γ却更接近于平均场理论模型,这可能是受顺磁区域的偶极相互作用影响。同时掺杂Tm³⁺后,在7 T磁场下的磁熵变值由6.19 J·kg^-1·K^-1减小到4.99 J·kg^-1·K...     

La0.6Sr0.4Co1-yFeyO3钙钛矿复合氧化物的GNP法合成与导电性能

采用甘氨酸-硝酸盐(GNP)法合成出La_0.6Sr_0.4Co_1-yFe_yO₃(y=0～1.0)体系复合氧化物,对合成产物的结构、烧结性能和导电性进行了表征.研究结果表明,不同n(Co)/n(Fe)比的合成粉料中形成菱形六面体钙钛矿结构,合成粉料的颗粒细小均匀.在室温～900℃范围内,La_0.6Sr_0.4CoO₃(y=0)的电导率随温度的升高而单调降低,其它n(Co)/n(Fe)比的样品电导率随着温度升高到600℃附近时达到最大值.在低温段,La_0.6Sr_0.4Co_1-yFe_yO₃体系的导电行为符合小极化子导电机制,导电活化能随n(Co)/n(Fe)比的降低而增大.与常规固相合成法相比,甘氨酸-硝酸盐法制备的La_0.6Sr_0.4Co_1-yFe_yO₃具有更高的烧结活性和电导率.     

在温和条件下巨磁阻材料La0.5Ba0.5MnO3的水热合成与表征

报道了在温和条件下巨磁阻材料La_0.5Ba_0.5MnO₃的水热合成.系统地研究了原料配比、碱度、时间和温度对产物合成的影响,在最佳合成条件下得到了结晶度较高的纯相,并通过XRD、DTA-TG、化学分析及碘量法对产物进行了表征.该化合物属立方晶系,晶胞参数为α=0.3913nm,V=0.05990nm₃,Mn的平均价态为3.5,在1T的外磁场下,磁阻比(MR)的极大值为29%.     

阴极支撑型固体氧化物燃料电池的制备与测试

采用固相反应法合成A缺位的(La_0.8Sr_0.2)_0.95MnO₃(LSM95)作为阴极材料,Zr_0.9Sc_0.1SO_1.95(SSZ)商业粉体作为电解质材料,溶胶-凝胶法合成的La_0.8Sr_0.2Cr_0.5Mn_0.5O₃-(LSCrM)作为阳极电催化材料,利用流延、共烧结及浸渍法得到结构为LSCrM-CeO₂|SSZ|3YSZ-LSM95的阴极支撑型固体氧化物燃料电池,分别在氢气气氛和甲烷气氛中进行电化学性能测试. 结果表明,浸渍0.11 g·cm ^-2 CeO₂的LSCrM-CeO₂|SSZ|3YSZ-LSM95单电池在以CH₄为燃料时,600、650、700、750和800 ^oC下的功率密度分别为1.68、4.70、12.40、28.08和54.78 mW·cm ^-2,表现出一定的电化学性能和较好的稳定性.     

In sight of K-deficient layered KxMnO2 cathode for potassium-ions batteries

Potassium-ions batteries(PIBs)are attracting increasing attention as up-and-coming youngster in largescale grid-level energy storage benefiting from its low-cost and high energy density.Nevertheless,enough researches regarding indispensable cathode materials for PIBs are badly absent.Herein,we synthesize K-deficient layered manganese-based oxides(P2-K_0.21MnO₂ and P3-K_0.23MnO₂)and investigate them as cathode of PIBs for the first time.As the newcomer of potassium-containing layered manganese-based oxides(K_xMnO₂)group,P2-K_0.21MnO₂ delivers high discharge capacity of 99.3 mAh g^-1 and P3-K_0.23MnO₂ exhibits remarkable capacity retention rate of 75.5%.Besides,in-situ XRD and ex-situ XRD measurements reveal the reversible phase transition of P2-K_0.21MnO₂ and P3-K_0.23MnO₂ with the potassium-ions extraction and reinsertion,respectively.This work contributes to a better understanding for the potassium storage in K-deficient layered K_xMnO₂(x≤0.23),possessing an important basic scientific significance for the exploitation and application of layered K_xMnO₂ in PIBs.     

混合配体配合物胍基脒基镧的合成及性能

La₂O₃薄膜材料应用广泛，而制备La₂O₃薄膜的前驱体合成面临着挑战，多数现有前驱体热稳定性差、合成路线复杂或者成本高等问题。因此，本文报道了混配型和均配型的胍基、脒基镧配合物二(N,N′-二异丙基-甲胺基胍基)一(N,N′-二异丙基戊基脒基)合镧(配合物1)和三(N,N′-二异丙基-甲胺基胍基)合镧(配合物2),通过¹H NMR,¹³C NMR表征结构；通过热重分析(TGA)研究所有配合物的热稳定性和挥发性。结果表明：配合物1在加热至170.0℃时，其蒸气压会急剧上升；在202.0℃能产生1.0 Torr的蒸气压；在260.0℃以下该配合物有良好的热稳定性。以上数据说明：该配合物比较好地满足CVD工艺条件，是一种潜在的化学气相沉积前驱体；通过CVD技术，在源加热温度210℃、沉积温度为260.0℃、沉积时间为10.0 min的条件下得到约11.9 nm薄膜，SEM和XPS分析了薄膜的形貌和成分，实验结果表明沉积的纳米薄膜为高纯的La₂     

La_(1-x)Rb_xMnO_3钙钛矿催化剂同时消除NO和碳烟的催化性能

采用溶剂热法制备了La_(1-x)Rb_xM n O_3(x=0、0.1、0.2、0.3)钙钛矿型复合金属氧化物催化剂,通过XRD、FT-IR、SEM、XPS和H_2-TPR等手段对催化剂进行表征,在微型固定床反应器上评价了其同时消除NO和碳烟的催化性能。结果表明,La_(1-x)Rb_xM n O_3催化剂具有单一的钙钛矿结构,样品中Mn物种以Mn~(3+)和Mn~(4+)的形式存在。与LaMn O_3催化剂相比,Rb~+部分取代La~(3+),催化剂体系中形成较多的高价Mn~(4+)和氧空位,其氧化还原性能提高,催化性能得到改善。随着Rb~+取代量的增加,NO转化率升高,碳烟燃烧温度降低。当x=0.3时,La_(0.7)Rb_(0.3)M n O_3催化剂上CO_2浓度峰值温度t_(max)为430℃,CO_2的选择性为99.0%;反应温度为429℃,NO转化率达到最大,为59.7%。     

Pd/La_(0.8)Ce_(0.2)MnO_3/ZSM-5的制备及其甲苯催化燃烧活性

以贵金属改性的钙钛矿为活性组分,通过等体积浸渍法制备了Pd/La0.8Ce0.2MnO3/ZSM-5催化剂,并采用XRD、BET、SEM和H2-TPR等技术对催化剂进行了表征。在固定床反应器上,对Pd/La0.8Ce0.2MnO3/ZSM-5催化剂上的甲苯为目标污染物的催化燃烧进行了研究,考察了焙烧温度、负载量及ZSM-5的性质对其催化活性的影响。结果表明,所得到Pd/La0.8Ce0.2MnO3催化剂仍保持钙钛矿型结构,Pd均匀的分布在催化剂表面,有利于催化剂活性的提高。当ZSM-5硅铝原子比为25、La0.8Ce0.2MnO3负载量为20%、焙烧温度为750℃时,La0.8Ce0.2MnO3/ZSM-5上甲苯的起燃温度和完全转化温度分别为200和279℃;加入0.3%的Pd后,Pd/La0.8Ce0.2MnO3/ZSM-5的催化活性明显提高,甲苯起燃温度下降了90℃,完全转化温度可低至230℃。     

Preparation of dense, ultra-thin MIEC ceramic membranes by atmospheric spray-pyrolysis technique

Dense ceramic mixed ionic and electronic conducting membranes have been deposited by atmospheric spray-pyrolysis technique onto porous ceramic substrates. Perovskite oxide layers, i.e. manganites La_1−xSr_xMnO₃, ferrites La_1−xSr_xFe_1−y(Co,Ni)_yO₃, gallates La_1−xSr_xGa_1−y(Co,Ni,Fe)_yO₃, cobaltites La_1−xSr_xCoO₃ and related perovskites such as lanthanum nickelate La₂NiO₄ layers have been prepared. The structure, morphology and composition of the layers were characterised by XRD, SEM and WDS, respectively. Density and gas tightness of the layers were studied as a function of deposition process parameters, film thickness (from 0.5 to 3 μm) and preparation procedure. The presence of cracks and defects due to thermo-mechanical stresses applied during or after the preparation process were correlated with the membrane composition and the corresponding thermal expansion coefficient differences between substrates and membranes.     

Structural and magnetic properties of thin manganite films grown on silicon substrates

Polycrystalline La_0.7Sr_0.3MnO₃ manganite thin films were grown on silicon substrates covered by SiO_x amorphous native oxide. Unusual splitting of the manganite layer was found: on the top of an intermediate layer characterised by lower crystalline order, a magnetic robust layer is formed. Curie temperatures of about 325 K were achieved for 70 nm thick films. A strong room temperature XMCD signal was detected indicating high spin polarisation near the surface.     

纯相Li_2MnO_3薄膜的制备及作为锂离子电池正极材料的电化学行为

采用固相烧结法制备了纯相Li2MnO3正极材料及靶材,采用脉冲激光沉积(PLD)法在氧气气氛、不同温度下沉积了Li2MnO3薄膜.通过X射线衍射(XRD)和拉曼(Raman)光谱表征了薄膜的晶体结构,采用扫描电镜(SEM)观察薄膜形貌及厚度,利用电化学手段测试了Li2MnO3薄膜作为锂离子电池正极材料性能.结果表明,PLD方法制备的纯相Li2MnO3薄膜随着沉积温度升高薄膜结晶性变好.25℃沉积的薄膜难以可逆充放电,400℃沉积的薄膜具有较高的电化学活性和循环稳定性.相对于粉末材料,400与600℃制备的Li2MnO3薄膜电极平均放电电位随着循环次数的衰减速率明显低于相应的粉体材料.     

Thin Film of Perovskite Oxide with Atomic Scale p-n Junctions

Thin films of perovskite manganese oxide La_0.66Ca_0.29K_0.05MnO₃(LCKMO) on Au/ITO(ITO=indium tin oxide) substrates were prepared by off-axis radio frequency magnetron sputtering and characterized by X-ray diffraction( XRD), high-resolution transmission electron microscopy(HRTEM), and conductive atomic force microscopy (C-AFM) at room temperature. The thin films with thickness ranged from 100 nm to 300 nm basically show cubic structures with a=0.3886 nm, the same as that of the raw material used, but the structures are highly modulated. C-AFM results revealed that the atomic scale p-n junction feature of the thin films was the same as that of the single crystals. The preparation of the thin films thus further confirms the possibility of their application extending from micrometer-sized single crystals to macroscopic thin film.     

Plasma chemical preparation and characterization of perovskite-type mixed oxides

The microwave plasma enhanced chemical vapour deposition (MPECVD) was applied for the preparation of perovskite-like mixed oxides, using either the metal acetylacetonates or metal nitrates as precursors. The same materials were prepared by the citrate method as reference substances. The obtained mixed oxides were calcined at 1100 °C, tested in the methane oxidation up to 1000 °C and characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), inductive coupled plasma–optical emissions spectroscopy (ICP–OES) and specific surface area (BET) determination. These studies revealed that LaMnO₃ with La³⁺ cation partly substituted by Sr, Ce and Ba cations and La_0.9Sr_0.1Co_0.9Fe_0.1O₃ calcined at 1100 °C seem to be highly active and stable catalysts in methane oxidation. In the case of LaMnO₃ and La_0.9Ce_0.1MnO₃ lowest light-off temperatures were reached with the catalysts prepared by the plasma method.     

等离子体在同时去除NOx和碳烟催化反应中的作用

采用程序升温反应(TPR)技术,研究了等离子体辅助同时催化去除富氧柴油机尾气中NO_x和碳烟(soot)的反应特性.研究结果表明,等离子体提高了同时去除NO_x-soot的催化反应活性,降低了碳烟的燃烧温度,使碳烟起燃温度从300 ℃降到280 ℃,燃尽温度从425 ℃降到380 ℃;同时,等离子体辅助提高了NO_x转化为N₂的效率,使催化选择性从1.12％提高到1.53％.本文还分别研究了在NO和O₂的环境中,有或没有等离子体作用下,碳烟在催化作用下的去除特性.等离子体作用使得NO在和O₂共存、只有NO和只有O₂存在的各种条件下,碳烟的催化燃烧活性都有不同程度的提高,促进了N₂的生成.此外,本文也对等离子体辅助同时催化去除NO_x-soot的机理进行了探讨.