浸渍LaNi0.6Fe0.4O3-δ纳米颗粒对Zr0.84Y0.16O2-δ- La0.8Sr0.2Cr0.5Fe0.5O3-δ透氧膜性能的影响

doi:10.15541/jim20170115

无机材料学报 ›› 2018, Vol. 33 ›› Issue (1): 14-18.DOI: 10.15541/jim20170115 CSTR: 32189.14.10.15541/jim20170115

所属专题：乘风破浪的新能源材料

浸渍LaNi_0.6Fe_0.4O_3-_δ纳米颗粒对Zr_0.84Y_0.16O_2-_δ- La_0.8Sr_0.2Cr_0.5Fe_0.5O_3-_δ透氧膜性能的影响

刘雪娇^1,2, 何振宇³, 吴昊¹, 骆婷¹, 孟夑¹, 陈初升³, 占忠亮¹

1. 中国科学院上海硅酸盐研究所, 上海 200050;
2. 中国科学院大学, 北京 100049;
3.中国科学技术大学材料科学与工程系, 合肥 230026

收稿日期:2017-03-15 修回日期:2017-05-11 出版日期:2018-01-23 网络出版日期:2017-12-15
作者简介:刘雪娇(1988-), 女, 博士研究生. E-mail: xuejiao8810@student. mail.sic.ac.cn
基金资助:
国家自然科学基金(51672298) National Natural Science Foundation of China (51672298)

Influence of Impregnated Nano-scale LaNi_0.6Fe_0.4O_3-_δ Particles on the Oxygen Permeation Performance of Zr_0.84Y_0.16O_2-_δ-La_0.8Sr_0.2Cr_0.5Fe_0.5O_3-_δ Composite Membranes

LIU Xue-Jiao^1,2, HE Zhen-Yu³, WU Hao¹, LUO Ting¹, MENG Xie¹, CHEN Chu-Sheng³, ZHAN Zhong-Liang¹

1. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China;
2. University of Chinese Academy of Sciences, Beijing 100049, China;
3. Department of Materials Sciences and Engineering, University of Science & Technology of China, Hefei 230026, China;

Received:2017-03-15 Revised:2017-05-11 Published:2018-01-23 Online:2017-12-15
Supported by:
National Natural Science Foundation of China (51672298)

摘要/Abstract

摘要：

采用流延-共压-共烧结法制备了具有多孔|致密|多孔Zr_0.84Y_0.16O_2-_δ-La_0.8Sr_0.2Cr_0.5Fe_0.5O_3-_δ (YSZ-LSCF)结构的透氧膜和多孔YSZ-LSCF|致密YSZ-LSCF|致密YSZ|致密YSZ-LSCF|多孔YSZ-LSCF结构的固体氧化物燃料电池。采用浸渍法在多孔层内壁上沉积了具有高催化活性的LaNi_0.6Fe_0.4O_3-_δ (LNF)纳米颗粒, 随着LNF浸渍量的提高, 会在多孔层内壁上形成连续的导电网格, 增加电化学反应活性位点, 进而显著改善电极性能。当LNF浸渍量为12wt%时, 电极性能达到最优, 在800℃时阴极和阳极极化阻抗分别为0.26和0.08 Ω∙cm², 在空气/CH₄梯度中氧渗透速率为7.6 mL/(cm²∙min), 比未浸渍前提高了14倍。阻抗谱分析表明空气侧氧还原反应中的电荷转移反应是氧渗透过程的速率控制步骤。

关键词: 透氧膜, 甲烷部分氧化, 纳米结构, 催化剂

Abstract:

This paper reported on the fabrication of tri-layered oxygen transport membranes, “porous|dense|porous” Zr_0.84Y_0.16O_2-δ-La_0.8Sr_0.2Cr_0.5Fe_0.5O_3-δ (YSZ-LSCF), by the tape casting, tape lamination and co-firing techniques. Catalytically active nano-scale particles of LaNi_0.6Fe_0.4O_3-δ (LNF) were impregnated into the porous scaffolds. In order to quantatively determine the resistances of the oxygen reduction or evolution reactions against oxygen permeation, an additional dense YSZ layer was introduced inside the dense YSZ-LSCF permeation layer. Electrochemical measurements on the resulting five-layered solid oxide fuel cells showed a large reduction in the interfacial polarization resistances at the presence of these LNF catalysts, with the lowest values observed at the LNF loadings of 12wt%. In particular, the cathodic and anodic polarization resistances were 0.26 and 0.08 Ω·cm² at 800℃, respectively. The oxygen permeation flux under the air/CH₄ gradient was 7.6 mL/(cm²·min), which was 14 times higher than the measured value for the blank YSZ-LSCF membrane. Further impedance analysis indicated that the charge transfer step during oxygen reduction may limit the overall oxygen permeation process.

Key words: oxygen transport membranes, partial oxidation of methane, nanostructures, catalysts

中图分类号:

TQ028.8

刘雪娇, 何振宇, 吴昊, 骆婷, 孟夑, 陈初升, 占忠亮. 浸渍LaNi_0.6Fe_0.4O_3-_δ纳米颗粒对Zr_0.84Y_0.16O_2-_δ- La_0.8Sr_0.2Cr_0.5Fe_0.5O_3-_δ透氧膜性能的影响[J]. 无机材料学报, 2018, 33(1): 14-18.

LIU Xue-Jiao, HE Zhen-Yu, WU Hao, LUO Ting, MENG Xie, CHEN Chu-Sheng, ZHAN Zhong-Liang. Influence of Impregnated Nano-scale LaNi_0.6Fe_0.4O_3-_δ Particles on the Oxygen Permeation Performance of Zr_0.84Y_0.16O_2-_δ-La_0.8Sr_0.2Cr_0.5Fe_0.5O_3-_δ Composite Membranes[J]. Journal of Inorganic Materials, 2018, 33(1): 14-18.

图/表 5

图1 透氧膜(a)、燃料电池(b)及其多孔电极(c)~(f)微观结构的扫描电镜照片

Fig. 1 SEM images of (a) OTM, (b) SOFC, (c) L4, (d) L8, (e) L12, and (f) L16

图2 (a) L0和(b) L12样品在空气/空气中的阻抗谱

Fig. 2 EIS plots of (a) L0 and (b) L12 tested at air/air gradients

图3 (a) L0和(b) L12样品在空气/甲烷气氛中的阻抗谱

Fig. 3 EIS plots of (a) L0 and (b) L12 tested at air/CH4 gradients

图4 (a) L0和(b) L12样品在空气/甲烷气氛中的伏安曲线

Fig. 4 Voltage-current curves of (a) L0 and (b) L12 tested at air/CH4 gradients

图5 不同LNF含量时透氧膜的(a)阻抗数值和(b)氧渗透速率与开路电压

Fig. 5 (a) Resistances and (b) oxygen permeation flux & open circuit voltage of OTMs with varied LNF loadings

参考文献 13

[1]	CHEN TING, JIANG WAN, JIANG WERI-HUI, et al.Research progress in improvement of oxygen permeation properties for dual-phase mixed conducting membranes.Journal of Inorganic Materials, 2015, 30(12): 1233-1242.
[2]	THURSFIELD A, METCALFE I S.The use of dense mixed ionic and electronic conducting membranes for chemical production.Journal of Materials Chemistry, 2004, 14(16): 2475-2485.
[3]	DIXON A G.Recent research in catalytic inorganic membrane reactors.International Journal of Chemical Reactor Engineering, 2003, 1(1): 563-568.
[4]	STEELE B H.Oxygen ion conductors and their technological applications. Materials Science and Engineering, 1992, 13(2): 79-87.
[5]	GEFFROYA P M, FOULETIER J, RICHET N, et al.Rational selection of MIEC materials in energy production processes.Chemical Engineering Science, 2013, 87(9): 408-433.
[6]	YUAN RONG-HUA, HE WEI, ZHANG YU, et al.Preparation and characterization of supported planar Zr0.84Y0.16O1.92- La0.8Sr0.2Cr0.5Fe0.5O3-δ composite membrane.Journal of Membrane Science, 2016, 499: 335-342.
[7]	ZHANG YU, YUAN RONG-HUA, GAO JIAN-FEMG, et al.Oxygen permeation properties of supported planar Zr0.84Y0.16O1.92- La0.8Sr0.2Cr0.5Fe0.5O3-δ composite membranes.Separation and Purification Technology, 2016, 166: 142-147.
[8]	ZHANG YU, YUAN RONG-HUA, HE ZHEN-YU, et al.Phase inversion tape casting and oxygen permeation properties of supported planar Zr0.84Y0.16O1.92-La0.8Sr0.2Cr0.5Fe0.5O3-δ composite membrane. Solid State Ionics, 2016, 288: 342-346.
[9]	HE WEI, HUANG HUA, CHEN MING, et al.Stability and oxygen transport property of La0.8Sr0.2Cr0.5Fe0.5O3-δ.Solid State Ionics, 2014, 260: 86-89.
[10]	SEREDA V V, TSVETKOV D S, IVANOV I L, et al.Oxygen nonstoichiometry, defect structure and related properties of LaNi0.6Fe0.4O3-δ. Journal of Materials Chemistry, 2015, 3(11): 6028-6037.
[11]	LUO TING, LIU XUE-JIAO, MENG XIE, et al.In situ formation of LaNi0.6Fe0.4O3-δ-carbon nanotube hybrids as anodes for direct- methane solid oxide fuel cells.Journal of Power Sources, 2015, 299: 472-479.
[12]	LIU XUE-JIAO, HAN DA, ZHOU YU-CUN, et al.Sc-substituted La0.6Sr0.4FeO3-δ mixed conducting oxides as promising electrodes for symmetrical solid oxide fuel cells.Journal of Power Sources, 2014, 246: 457-463.
[13]	FERGUS J W.Electrolytes for solid oxide fuel cells.Journal of Power Sources, 2006, 162(1): 30-40.

[1]	王俊卜, 黄泽皑, 杨茗凯, 蒙颖, 周明炜, 周莹. 甲烷转化用抗积碳催化材料研究进展[J]. 无机材料学报, 2026, 41(6): 739-750.
[2]	李娜, 魏进, 曹锐霄, 刘玉, 黄贵文, 肖红梅. 自研正仲氢转化催化剂的催化测试分析及批量制备工艺优化[J]. 无机材料学报, 2026, 41(5): 645-652.
[3]	薛新燕, 张晓卫, 鲁恒, 李世杰, 张卫珂, 曾少华. 钴-镁协同纳米洋葱碳催化剂的制备及低温催化氨分解制氢性能[J]. 无机材料学报, 2026, 41(4): 500-508.
[4]	黄应贺, 黄仁兴, 石宇星, 雷一杰, 于涛, 王诚, 顾军. 利用介孔碳的限域效应提升氧还原反应中Pt催化剂的耐久性[J]. 无机材料学报, 2026, 41(3): 289-294.
[5]	任先培, 李超, 胡启威, 向晖, 彭跃红. 金属/过渡金属化合物莫特-肖特基析氢催化剂研究进展[J]. 无机材料学报, 2026, 41(2): 137-149.
[6]	邬博宇, 张深根, 张生杨, 刘波, 张柏林. CeO₂对MnO_x催化剂低温脱硝性能的影响及其机理研究[J]. 无机材料学报, 2026, 41(1): 87-95.
[7]	刘江平, 管鑫, 唐振杰, 朱文杰, 罗永明. 含氮挥发性有机化合物催化氧化的研究进展[J]. 无机材料学报, 2025, 40(9): 933-943.
[8]	郭子玉, 朱云洲, 王力, 陈健, 李红, 黄政仁. Zn²⁺催化剂对酚醛树脂/乙二醇制备多孔碳微观孔结构的影响[J]. 无机材料学报, 2025, 40(5): 466-472.
[9]	李建军, 陈芳明, 张梨梨, 王磊, 张丽亭, 陈慧雯, 薛长国, 徐良骥. CoFe₂O₄/MgAl-LDH催化剂活化过氧一硫酸盐促进抗生素降解[J]. 无机材料学报, 2025, 40(4): 440-448.
[10]	信震宇, 郭瑞华, 乌仁托亚, 王艳, 安胜利, 张国芳, 关丽丽. Pt-Fe/GO纳米催化剂的制备及其电催化乙醇氧化性能研究[J]. 无机材料学报, 2025, 40(4): 379-387.
[11]	孙树娟, 郑南南, 潘昊坤, 马猛, 陈俊, 黄秀兵. 单原子催化剂制备方法的研究进展[J]. 无机材料学报, 2025, 40(2): 113-127.
[12]	李薛茹, 马哲杰, 郭宇杰, 李平. 载体特性对Pt/C催化剂上离聚物覆盖度及氧还原性能的影响[J]. 无机材料学报, 2025, 40(12): 1395-1404.
[13]	赵丽娟, 谭哲, 张晓光, 蒋国赛, 陶然, 潘德安. 废加氢催化剂颗粒分级数值模拟研究[J]. 无机材料学报, 2025, 40(12): 1387-1394.
[14]	刘盼盼, 姚鹏, 刘栩孜, 屈丽, 曾路, 宋兆华, 焦毅, 王健礼, 陈耀强. MnO_x/CeO₂-ZrO₂复合氧化物的构筑及其在碳烟氧化中的应用[J]. 无机材料学报, 2025, 40(11): 1300-1308.
[15]	李娜, 曹锐霄, 魏进, 周晗, 肖红梅. 铁基正仲氢转化催化剂的影响因素[J]. 无机材料学报, 2025, 40(1): 47-52.

浸渍LaNi_0.6Fe_0.4O_3-_δ纳米颗粒对Zr_0.84Y_0.16O_2-_δ- La_0.8Sr_0.2Cr_0.5Fe_0.5O_3-_δ透氧膜性能的影响

Influence of Impregnated Nano-scale LaNi_0.6Fe_0.4O_3-_δ Particles on the Oxygen Permeation Performance of Zr_0.84Y_0.16O_2-_δ-La_0.8Sr_0.2Cr_0.5Fe_0.5O_3-_δ Composite Membranes

RichHTML

PDF (PC)