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1.
陈蓉  马桂林  李宝宗 《无机化学学报》2002,18(12):1200-1204
用高温固相反应法首次合成了非化学计量组成的Ba1.03Ce0.8Dy0.2O3-α固体电解质样品,对其进行了X-射线衍射晶体结构测定,该样品为钙钛矿型斜方晶单相结构。分别用气体浓差电池方法和氢泵(氢的电化学透过)方法研究了它在600~1000℃下的质子和氧离子导电特性,并与化学计量组成的BaCe0.8Dy0.2O3-α固体电解质样品进行了比较。实验结果表明,Ba1.03Ce0.8Dy0.2O3-α的质子导电性优于BaCe0.8Dy0.2O3-α。Ba1.03Ce0.8Dy0.2O3-α在600~1000℃下氢气氛中的质子迁移数约为1,几乎是一个纯质子导体,而BaCe0.8Dy0.2O3-α在氢气氛中600~800℃下是一个纯质子导体,在高于800℃时是一个质子与电子的混合导体。这两个样品在氧气氛中均是氧离子与电子空穴的混合导体,具有几乎相同的氧离子迁移数。  相似文献   

2.
采用高温固相法制备了BaCe0.8Lu0.2O3-α质子导体。运用X射线衍射仪(XRD)、扫描电镜(SEM)对该材料的物相结构、微观形貌进行了表征。在500~900℃温度范围内,应用交流阻抗谱和气体浓差电池方法研究了材料在不同气体气氛中的离子导电性和氢-空气燃料电池性能。结果表明,BaCe0.8Lu0.2O3-α材料为单一斜方晶结构,具有良好的致密性。在500~900℃温度范围内,干燥或湿润的氮气、空气和氧气中,材料的电导率随着氧分压增大稍有增大。在湿润的氢气中,材料表现为纯的质子导电性。在以该材料为固体电解质的氢-空气燃料电池条件下,材料表现为质子、氧离子和电子的混合导电性,其中离子导电性始终占主导;氢-空气燃料电池在900℃下的最大输出功率密度为92.2mW·cm-2,高于我们以前报道的BaCe0.8RE0.2O3-α(RE=Pr,Eu,Ho,Er,等)材料。  相似文献   

3.
用高温固相反应法制备了Ba0.95Ce0.8Ho0.2O3-α,X–射线衍射表明,该材料为单相钙钛矿型斜方晶结构。以该材料为固体电解质,多孔性铂为电极,用气体浓差电池方法和交流阻抗谱方法分别测定了材料在600 ~ 1000℃温度范围,潮湿氢气、干燥和潮湿的空气中的离子迁移数和电导率,研究了该材料的离子导电性,并与BaCe0.8Ho0.2O3-α作了比较。结果表明,在600 ~ 700 ℃、潮湿氢气中,Ba0.95Ce0.8Ho0.2O3-α是纯的质子导体,质子迁移数为1;在800 ~ 1000 ℃,是质子和电子的混合导体,质子迁移数为0.97 ~ 0.93。而BaCe0.8Ho0.2O3-α在潮湿氢气中几乎是纯的质子导体,在600 ~ 900 ℃,质子迁移数为1;在1000 ℃,质子迁移数为为0.99。在600 ~ 1000℃温度范围内、干燥的空气中,它们都是氧离子和电子空穴的混合导体,氧离子迁移数分别为0.24 ~ 0.33和0.17 ~ 0.30;在潮湿的空气中,它们都是质子、氧离子和电子空穴的混合导体,质子迁移数分别为0.11 ~ 0.00 和0.09 ~ 0.01,氧离子迁移数分别为0.41 ~ 0.33和0.27 ~ 0.30。在潮湿的氢气和空气中,在600 ~ 800 ℃温度范围内,Ba0.95Ce0.8Ho0.2O3-α的质子电导率高于BaCe0.8Ho0.2O3-α,但在800 ~ 1000 ℃温度范围内,Ba0.95Ce0.8Ho0.2O3-α的质子电导率则低于BaCe0.8Ho0.2O3-α。在600 ~ 1000 ℃温度范围内、潮湿和干燥的空气中,氧离子电导率总是高于BaCe0.8Ho0.2O3-α。  相似文献   

4.
以高温固相反应法合成了BaCe0.7Zr0.2La0.1O3-α陶瓷。粉末XRD结果表明,该陶瓷材料为单一钙钛矿型BaCeO3斜方晶结构。以陶瓷材料为固体电解质、多孔性铂为电极,采用交流阻抗谱技术和气体浓差电池方法分别测定了材料在500~900 ℃下,干燥空气、湿润空气和湿润氢气中的电导率以及离子迁移数,研究了材料的离子导电特性。结果表明,在500~900 ℃下干燥空气中,陶瓷材料的最大电导率为1.8 mS·cm-1,氧离子迁移数为0.14~0.04,是一个氧离子与电子空穴的混合导体。在湿润空气中,陶瓷材料的最大电导率为2.0 mS·cm-1,质子迁移数为0.48~0,氧离子迁移数为0.25~0.10,是质子、氧离子和电子空穴的混合导体。在湿润氢气中,陶瓷材料的最大电导率为3.6 mS·cm-1。在500~700 ℃温度范围内,陶瓷材料的质子迁移数为1,是纯的质子导体;而在800~900 ℃温度范围内,陶瓷材料的质子迁移数为0.93~0.91,是质子与电子的混合导体,质子电导占主导。  相似文献   

5.
本文通过高温固相反应合成了Ba0.95Ce0.90Y0.10O3-α固体电解质,测定了该固体电解质高温(600~1000℃)下的氢的电化学透过(氢气泵)速度。结果表明,该固体电解质在本实验条件下具有良好的质子导电性,其质子迁移数为0.8~1,在600~700℃的较低温度下,几乎显示纯粹的质子导电性  相似文献   

6.
仇立干  王茂元 《化学学报》2010,68(3):276-282
用高温固相反应法合成了非化学计量组成的Ba1.03Ce0.5Zr0.4La0.1O3-α质子导体. 粉末X射线衍射(XRD)结果表明, 该材料为单一钙钛矿型BaCeO3斜方晶结构, 在高温下、CO2或水蒸气气氛中具有较高的稳定性. 扫描电子显微镜(SEM)观察分析表明, 材料经1550 ℃烧结20 h非常致密. 在500~900 ℃温度范围内, 用交流阻抗谱技术测定了材料在湿润氢气和湿润空气气氛中的电导率; 用气体浓差电池方法测定了材料在湿润氢气、湿润空气气氛中和氢-空气燃料电池条件下的离子迁移数, 研究了材料的离子导电特性, 并与化学计量组成的BaCe0.5Zr0.4La0.1O3-α材料进行了比较. 结果表明, 在500~900 ℃温度范围内、湿润氢气气氛中, Ba1.03Ce0.5Zr0.4La0.1O3-α材料的质子迁移数为1, 是一个纯质子导体. 在湿润空气气氛中, 材料的氧离子迁移数为0.688~0.170, 质子迁移数为0.218~0.017, 是一个氧离子、质子和电子空穴的混合导体. 在氢-空气燃料电池条件下, 材料的离子(氧离子+质子)迁移数为0.990~0.796, 是一个氧离子、质子和电子的混合导体. 与化学计量组成的BaCe0.5Zr0.4La0.1O3-α材料相比较, 在相同实验条件下非化学计量组成的Ba1.03Ce0.5Zr0.4La0.1O3-α材料具有较高的电导率和离子迁移数.  相似文献   

7.
刘荣梅  马桂林  周丽  陈蓉 《化学学报》2005,63(6):491-496
以湿化学法制得Zr(OH)4和Sm(OH)3的共沉淀为前驱体, 在碱性介质中用水热法合成了(ZrO2)0.86(Sm2O3)0.14及(ZrO2)0.88(Sm2O3)0.12纳米粉体. 将纳米粉体在较低温度(1450 ℃)下烧结制得了致密的固体电解质陶瓷样品, 比通常高温固相反应法采用的烧结温度(>1600 ℃)降低了150 ℃以上. XRD测定结果表明, (ZrO2)0.86(Sm2O3)0.14纳米粉体及其烧结体均为立方相, 但(ZrO2)0.88(Sm2O3)0.12纳米粉体为立方相, 它的烧结体为立方相和单斜相的混合相. 用交流阻抗谱法、氧浓差电池法及氧泵(氧的电化学透过)法研究了(ZrO2)0.86(Sm2O3)0.14陶瓷样品在600~1000 ℃下的离子导电特性. 结果表明, 该陶瓷样品在600~1000 ℃下氧离子迁移数为1, 氧离子电导率的最大值为3.2×10-2 S•cm-1, 是一个优良的氧离子导体; 它的氧泵性能明显地优于YSZ.  相似文献   

8.
通过高温固相合成法首次合成了La2Mo1.8Ga0.2O9陶瓷样品. 粉末XRD结果表明, 该样品为单一立方相La2Mo2O9结构. 以陶瓷样品为固体电解质、多孔性铂为电极, 采用交流阻抗谱、气体浓差电池、氧泵等方法研究了样品在600~1000 ℃下各种气氛中的离子导电特性. 结果表明, 氧浓差电池电动势的实测值与理论值吻合得很好, 氧离子迁移数为1, 表明该陶瓷样品在该温度下氧气气氛中为一纯氧离子导体; 氧泵(氧的电化学透过)实验结果进一步证实了该样品在氧气气氛中为一纯氧离子导体; 在氧分压p(O2)=10-5~105 Pa的高氧分压气氛中, 电导率与氧分压变化基本无关, 表明在该氧分压范围内样品为纯离子导体, 这与氧浓差电池电动势测定结果相吻合; 在低氧分压为10-5~10-15 Pa范围内, 总电导率随氧分压降低而稍有升高, 表明在该氧分压范围样品为氧离子与电子的混合导体; 在600~1000 ℃下氧离子电导率>10-2 S•cm-1, 显著高于母体La2Mo2O9的氧离子电导率, 1000 ℃时的氧离子电导率为0.07 S•cm-1.  相似文献   

9.
许睿  潘博  张峰  马桂林  仇立干 《化学学报》2006,64(24):2442-2446
通过高温固相合成法首次合成了La2Mo1.8Ga0.2O9陶瓷样品. 粉末XRD结果表明, 该样品为单一立方相La2Mo2O9结构. 以陶瓷样品为固体电解质、多孔性铂为电极, 采用交流阻抗谱、气体浓差电池、氧泵等方法研究了样品在600~1000 ℃下各种气氛中的离子导电特性. 结果表明, 氧浓差电池电动势的实测值与理论值吻合得很好, 氧离子迁移数为1, 表明该陶瓷样品在该温度下氧气气氛中为一纯氧离子导体; 氧泵(氧的电化学透过)实验结果进一步证实了该样品在氧气气氛中为一纯氧离子导体; 在氧分压p(O2)=10-5~105 Pa的高氧分压气氛中, 电导率与氧分压变化基本无关, 表明在该氧分压范围内样品为纯离子导体, 这与氧浓差电池电动势测定结果相吻合; 在低氧分压为10-5~10-15 Pa范围内, 总电导率随氧分压降低而稍有升高, 表明在该氧分压范围样品为氧离子与电子的混合导体; 在600~1000 ℃下氧离子电导率>10-2 S•cm-1, 显著高于母体La2Mo2O9的氧离子电导率, 1000 ℃时的氧离子电导率为0.07 S•cm-1.  相似文献   

10.
用溶胶凝胶法制备了复合固体电解质xNH4PO3-SiO2(x=1,2,4),并研究了该电解质在125~250 ℃范围内的导电性能。复合电解质的相结构分析表明,NH4PO3和SiO2在溶胶凝胶法制备过程中没有发生化学反应;复合电解质的电导率随着NH4PO3含量增大而提高,并与NH4PO  相似文献   

11.
K3InF6 is synthesized by a sol-gel route starting from indium and potassium acetates dissolved in isopropanol in the stoichiometry 1:3, with trifluoroacetic acid as fluorinating agent. The crystal structures of the organic precursors were solved by X-ray diffraction methods on single crystals. Three organic compounds were isolated and identified: K2InC10O10H6F9, K3InC12O14H4F18 and K3InC12O12F18. The first one, deficient in potassium in comparison with the initial stoichiometry, is unstable. In its crystal structure, acetate as well as trifluoroacetate anions are coordinated to the indium atom. The two other precursors are obtained, respectively, by quick and slow evaporation of the solution. They correspond to the final organic compounds, which give K3InF6 by decomposition at high temperature. The crystal structure of K3InC12O14H4F18 is characterized by complex anions [In(CF3COO)4(OHx)2](5−2x)− and isolated [CF3COOH2−x](x−1)− molecules with x=2 or 1, surrounded by K+ cations. The crystal structure of K3InC12O12F18 is only constituted by complex anions [In(CF3COO)6]3− and K+ cations. For all these compounds, potassium cations ensure only the electroneutrality of the structure. IR spectra of K2InC10O10H6F9 and K3InC12O12F18 were also performed at room temperature on pulverized crystals.  相似文献   

12.
一些具有NASICON型网格结构的固体电解质具有高的电导率和好的稳定性,NASICON的意思是Na Super Ionic Conductor[1]。当NaZr2(PO4)3中P5 被Si4 部分取代时便可以得到具有NASICON结构的Na1 xZr2SixP3-xO12体系,其具有高的钠离子电导率。然而有相同结构的Li1 xZr2SixP3-xO12体系的离子电导率却很低,这是因为Li 半径太小,而NASICON三维网格结构的离子通道太大,两者不匹配而使电导率下降[2]。但当LiZr2(PO4)3中Zr4 被离子半径小些的Ti4 取代,所得LiTi2(PO4)3的通道就与Li 半径相匹配,适合于锂离子的迁移,从而使其电导率…  相似文献   

13.
The compound previously reported as Ba2Ti2B2O9 has been reformulated as Ba3Ti3B2O12, or Ba3Ti3O6(BO3)2, a new barium titanium oxoborate. Small single crystals have been recovered from a melt with a composition of BaTiO3:BaTiB2O6 (molar ratio) cooled between 1100°C and 850°C. The crystal structure has been determined by X-ray diffraction: hexagonal system, non-centrosymmetric space group, a=8.7377(11) Å, c=3.9147(8) Å, Z=1, wR(F2)=0.039 for 504 unique reflections. Ba3Ti3O6(BO3)2 is isostructural with K3Ta3O6(BO3)2. Preliminary measurements of nonlinear optical properties on microcrystalline samples show that the second harmonic generation efficiency of Ba3Ti3O6(BO3)2 is equal to 95% of that of LiNbO3.  相似文献   

14.
The ferroelectric ceramics of Bi4Ti3O12, SrBi4Ti4O15, and lanthanum-doped Bi4Ti3O12-SrBi4Ti4O15 were synthesized, and their Raman spectra were investigated. La-doping resulted in the enlargement of remnant polarization of Bi4Ti3O12-SrBi4Ti4O15. The structure of the Bi2O2 layers and TiO6 octahedra of the intergrowth was found to be different from those of Bi4Ti3O12 and SrBi4Ti4O15. La3+ ions exhibit pronounced selectivity for the occupation of A site as La content is lower than 0.50, and tend to be incorporated into Bi2O2 layers when the La content is higher than 0.50. Lanthanum substitution brings about the structural phase transition in Bi4Ti3O12-SrBi4Ti4O15. The variation of ferroelectric property may be attributed to combined contribution from the decreasing of the oxygen vacancies, the relaxation of the lattice distortion, the destroying of the insulation and the space charge compensation effects of the Bi2O2 slabs.  相似文献   

15.
A new oxide, Bi14Sr21Fe12O61, with a layered structure derived from the 2212 modulated type structure Bi2Sr3Fe2O9, was isolated. It crystallizes in the I2 space group, with the following parameters: a=16.58(3) Å, b=5.496(1) Å, c=35.27(2) Å and β=90.62°. The single crystal X-ray structure determination, coupled with electron microscopy, shows that this ferrite is the m=5 member of the [Bi2Sr3Fe2O9]m[Bi4Sr6Fe2O16] collapsed family. This new collapsed structure can be described as slices of 2212 structure of five bismuth polyhedra thick along , shifted with respect to each other and interconnected by means of [Bi4Sr6Fe2O16] slices. The latter are the place of numerous defects like iron or strontium for bismuth substitution; they can be correlated to intergrowth defects with other members of the family.  相似文献   

16.
Thin crystals of La2O3, LaAlO3, La2/3TiO3, La2TiO5, and La2Ti2O7 have been irradiated in situ using 1 MeV Kr2+ ions at the Intermediate Voltage Electron Microscope-Tandem User Facility (IVEM-Tandem), Argonne National Laboratory (ANL). We observed that La2O3 remained crystalline to a fluence greater than 3.1×1016 ions cm−2 at a temperature of 50 K. The four binary oxide compounds in the two systems were observed through the crystalline-amorphous transition as a function of ion fluence and temperature. Results from the ion irradiations give critical temperatures for amorphisation (Tc) of 647 K for LaAlO3, 840 K for La2Ti2O7, 865 K for La2/3TiO3, and 1027 K for La2TiO5. The Tc values observed in this study, together with previous data for Al2O3 and TiO2, are discussed with reference to the melting points for the La2O3-Al2O3 and La2O3-TiO2 systems and the different local environments within the four crystal structures. Results suggest that there is an observable inverse correlation between Tc and melting temperature (Tm) in the two systems. More complex relationships exist between Tc and crystal structure, with the stoichiometric perovskite LaAlO3 being the most resistant to amorphisation.  相似文献   

17.
Single crystals of Ca3CuRhO6, Ca3Co1.34Rh0.66O6 and Ca3FeRhO6 were synthesized by high temperature flux growth in molten K2CO3 and structurally characterized by single crystal X-ray diffraction. While Ca3Co1.34Rh0.66O6 and Ca3FeRhO6 crystallize with trigonal (rhombohedral) symmetry in the space group , Z=6: Ca3Co1.34Rh0.66O6a=9.161(1) Å, c=10.601(2) Å; Ca3FeRhO6a=9.1884(3) Å, c=10.7750(4) Å; Ca3CuRhO6 adopts a monoclinic distortion of the K4CdCl6 structure in the space group C2/c, Z=4: a=9.004(2) Å, b=9.218(2) Å, c=6.453(1) Å, β=91.672(5). All crystals of Ca3CuRhO6 examined were twinned by pseudo-merohedry. Ca3CuRhO6, Ca3Co1.34Rh0.66O6, and Ca3FeRhO6 are structurally related and contain infinite one-dimensional chains of alternating face-sharing RhO6 octahedra and MO6 trigonal prisms. In the monoclinic modification, the copper atoms are displaced from the center of the trigonal prism toward one of the rectangular faces adopting a pseudo-square planar configuration. The magnetic properties of Ca3CuRhO6, Ca3Co1.34Rh0.66O6, and Ca3FeRhO6 are discussed.  相似文献   

18.
The basic mercury(I) chromate(VI), Hg6Cr2O9 (=2Hg2CrO4·Hg2O), has been obtained under hydrothermal conditions (200 °C, 5 days) in the form of orange needles as a by-product from reacting elemental mercury and K2Cr2O7. Hydrothermal treatment of microcrystalline Hg6Cr2O9 in demineralised water at 200 °C for 3 days led to crystal growth of red crystals of the basic mercury(I, II) chromate(VI), Hg6Cr2O10 (=2Hg2CrO4·2HgO). The crystal structures were solved and refined from single crystal X-ray data sets. Hg6Cr2O9: space group P212121, Z=4, a=7.3573(12), b=8.0336(13), , 3492 structure factors, 109 parameters, R[F2>2σ(F2)]=0.0371, wR(F2 all)=0.0517; Hg6Cr2O10: space group Pca21, Z=4, a=11.4745(15), b=9.4359(12), , 3249 structure factors, 114 parameters, R[F2>2σ(F2)]=0.0398, wR(F2 all)=0.0625. Both crystal structures are made up of an intricate mercury-oxygen network, subdivided into single building blocks [O-Hg-Hg-O] for the mercurous compound, and [O-Hg-Hg-O] and [O-Hg-O] for the mixed-valent compound. Hg6Cr2O9 contains three different Hg22+ dumbbells, whereas Hg6Cr2O10 contains two different Hg22+ dumbbells and two Hg2+ cations. The HgI-HgI distances are characteristic and range between 2.5031(15) and 2.5286(9) Å. All Hg22+ groups exhibit an unsymmetrical oxygen environment. The oxygen coordination of the Hg2+ cations is nearly linear with two tightly bonded O atoms at distances around 2.07 Å. For both structures, the chromate(VI) anions reside in the vacancies of the Hg-O network and deviate only slightly from the ideal tetrahedral geometry with average Cr-O distances of ca. 1.66 Å. Upon heating at temperatures above 385 °C, Hg6Cr2O9 decomposes in a four-step mechanism with Cr2O3 as the end-product at temperatures above 620 °C.  相似文献   

19.
吴关  周盈科 《无机化学学报》2018,34(7):1333-1340
使用液相包覆工艺对LiNi_(0.8)Co_(0.15)Al_(0.05)O_2(NCA)材料进行FePO_4包覆改性,利用FePO_4优异的结构稳定性与热稳定性,对NCA的长期可靠性与安全性能进行改良。重点研究FePO_4包覆对NCA材料的改性效果,以及不同包覆量造成的NCA材料电化学性能差异。表面包覆的FePO_4保护层,能够防止NCA材料与电解液直接接触发生副反应,抑制长期循环过程中过渡金属离子的溶出,保持结构的长期稳定性。当包覆量为1.0%(w/w)时,NCA材料表现出最优的综合性能,充放电循环800次后,容量保持率依然高达95%,25℃下存储100 d后,容量保持率也高于95%,达到了兼顾能量密度、使用寿命及安全性能的理想效果。  相似文献   

20.
Two new compounds, La3Ru8B6 and Y3Os8B6, were synthesized by arc melting the elements. Their structural characterization was carried out at room temperature on as-cast samples by using X-ray diffractometry. According to X-ray single-crystal diffraction results these borides crystallize in Fmmm space group (no. 69), Z=4, a=5.5607(1) Å, b=9.8035(3) Å, c=17.5524(4) Å, ρ=8.956 Mg/m3, μ=25.23 mm−1 for La3Ru8B6 and a=5.4792(2) Å, b=9.5139(4) Å, c=17.6972(8) Å, ρ=13.343 Mg/m3, μ=128.23 mm−1 for Y3Os8B6. The crystal structure of La3Ru8B6 was confirmed from Rietveld refinement of X-ray powder diffraction data. Both La3Ru8B6 and Y3Os8B6 compounds are isotypic with the Ca3Rh8B6 compound and their structures are built up from CeCo3B2-type and CeAl2Ga2-type structural fragments taken in ratio 2:1. They are the members of structural series R(A)nM3n−1B2n with n=3 (R is the rare earth metal, A the alkaline earth metal, and M the transition metal). Structural and atomic parameters were also obtained for La0.94Ru3B2 compound from Rietveld refinement (CeCo3B2-type structure, P6/mmm space group (no. 191), a=5.5835(9) Å, c=3.0278(6) Å).  相似文献   

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