LSGM电解质/阳极界面产物的性能研究
|
摘要
La_(0.9)Sr_(0.1)Ga_(0.8)Mg_(0.2)O_(2.85)(简称LSGM)是一种优良的中温氧化物燃料电池(SOFC)电解质材料。本文将Ni_2O_3、CeO_2按不同的比例和LSGM混合并采用研磨—加压成型—烧结工艺处理后作为阳极材料；将阳极材料和电解质LSGM按质量比1：1的方法混合并烧结，模拟LSGM电解质／阳极界面产物，对其性能进行研究。研究了SOFC阳极与电解质的界面产物的结构、直流和交流电导率等。用扫描电镜(SEM)观察样品表面形貌、晶粒大小。发现LSGM表面有大而稀疏的孔洞，这对氧离子的传输提供了有利条件；含CeO_2的样品表面有很多裂缝，结构不稳定。含Ni_2O_3的样品结构致密，孔洞细小且密集，这有利于氧离子的传输，增加电导率；用XRD检测样品的相及生成的产物，XRD显示LSGM样品与LaGaO_3的相相同，均为斜方相钙钛矿结构，未见其它衍射峰产生，加入CeO_2或Ni_2O_3后相结构没有发生变化，说明除LSGM、Ni_2O_3、CeO_2的混合物外没有合成新的产物。用二端法分别对样品进行直流电导率及交流电导率测试。发现样品直流电导率随温度升高而增加，样品在600℃-800℃有较高的电导率。样品的交流电导率在中低频区(10Hz-100KHz)几乎没有变化，高频区(＞100KHz)响应明显，高频区LSGM电解质及含CeO_2的样品电导率随频率增加而升高；含Ni_2O_3的样品随频率增加而降低。
La_(0.9)Sr_(0.1)Ga_(0.8)Mg_(0.2)O_(2.85) ( LSGM ) is a perfect electrolyte for the middle- temperature solid oxide fuel cell. In this paper, LSGM and anode materials of the SOFC are prepared by technology of lapping - forming with pressure - sintering. The anode materials are prepared by mixture with LSGM and Ni2O3 or CeO2 according to different proportion. The characteristics of the LSGM /anode interface products are investigated by using the method of the simulation of interface products, the interface products of the electrolyte LSGM/ anode are formed by mixing the electrolyte LSGM and the materials of anode according to 1:1 and sintering them.
The crystal structure and DC, AC conductivity of the products of the interface of electrolyte/ anode are studied. The pattern and the size of the grain are examined by the SEM. Some big and sparse holes are seen on the surface of LSGM specimen, it's a advantage for the condition of oxygen-ion transmission. The holes on the surface of Ni2O3-doped interface products specimen are small and dense, the structure of the specimen is compact, it's favorable for the transmission of oxygen-ion and the conductivity of oxygen-ion is high in this specimen. Some crevice is found on the surface of CeO2-doped specimen, so the structure is not stable. XRD is used to analyze the phase and product. The results indicated that the LSGM is a rhombohedral phase and perovskite structure which is the same to the LaGaO3. No new peak of diffraction is found in these materials, so no new products is generated in the material except for the mixture of LSGM, Ni2O3 and CeO2. Two probe method is used in the testing of DC conductivity and AC conductivity. The results of DC conductivity showed that conductivity of the specimen increased with rising of temperature. Conductivity is high in the range of 600 C -800 C. The AC conductivity of the specimen is not variable in the region of low and middle frequency, which is from10Hz to100KHz. The response of AC conductivity is sharp in the range which frequency is higher then 100KHz, the AC conductivity of LSGM and CeO2-doped specimen increased with the rise of frequency while Ni2O3-doped specimen reduced when the frequency is above 100KHz.
La_(0.9)Sr_(0.1)Ga_(0.8)Mg_(0.2)O_(2.85) ( LSGM ) is a perfect electrolyte for the middle- temperature solid oxide fuel cell. In this paper, LSGM and anode materials of the SOFC are prepared by technology of lapping - forming with pressure - sintering. The anode materials are prepared by mixture with LSGM and Ni2O3 or CeO2 according to different proportion. The characteristics of the LSGM /anode interface products are investigated by using the method of the simulation of interface products, the interface products of the electrolyte LSGM/ anode are formed by mixing the electrolyte LSGM and the materials of anode according to 1:1 and sintering them.
The crystal structure and DC, AC conductivity of the products of the interface of electrolyte/ anode are studied. The pattern and the size of the grain are examined by the SEM. Some big and sparse holes are seen on the surface of LSGM specimen, it's a advantage for the condition of oxygen-ion transmission. The holes on the surface of Ni2O3-doped interface products specimen are small and dense, the structure of the specimen is compact, it's favorable for the transmission of oxygen-ion and the conductivity of oxygen-ion is high in this specimen. Some crevice is found on the surface of CeO2-doped specimen, so the structure is not stable. XRD is used to analyze the phase and product. The results indicated that the LSGM is a rhombohedral phase and perovskite structure which is the same to the LaGaO3. No new peak of diffraction is found in these materials, so no new products is generated in the material except for the mixture of LSGM, Ni2O3 and CeO2. Two probe method is used in the testing of DC conductivity and AC conductivity. The results of DC conductivity showed that conductivity of the specimen increased with rising of temperature. Conductivity is high in the range of 600 C -800 C. The AC conductivity of the specimen is not variable in the region of low and middle frequency, which is from10Hz to100KHz. The response of AC conductivity is sharp in the range which frequency is higher then 100KHz, the AC conductivity of LSGM and CeO2-doped specimen increased with the rise of frequency while Ni2O3-doped specimen reduced when the frequency is above 100KHz.
引文
[1] 姚思童，司秀丽，杨军，等．燃料电池的工作原理及其发展现状．沈阳工业大学学报[J]．1998，20(1)
[2] 沙其骞．SOFC燃料电池空气电极材料—La_(1-x)Sr_xMnO_3粉体的制备及性能．稀土[J]．1994，15(1)．
[3] 张传福，黎昌俊，曾德文，等．燃料电池及其结构材料．有色金属(冶炼部分)[J]．1998，3(47)
[4] 王永钤，赵志国，李立本，等．燃料电池固体电解质．洛阳师专学报[J]．2000，19(2)
[5] 梁广川，陈玉如，吴厚政，等．燃料电池固体氧化物电解质研究进展．硅酸盐通报[J]．1999．5．
[6] 杨浩，陈文涛．固体电解质研究的实验方法及原理．商都学坛[J]．1994，3(14)．
[7] 阎景旺，董永来，于春英，等．中温固体氧化物燃料电池阳极基底及负载型电解质薄膜的研制．无机材料学报[J]．2001．16(5)．
[8] 江义，李文钊，王世忠．La_(0.8)Sr_(0.2)MO_3／YSZ高温电极交流阻抗研究．化学进展[J]．1997，9(4)．
[9] 江义．固体氧化物燃料电池最新发展动态．电化学[J]1998，4(4)．
[10] Ishihara T, Matsuda H,Takita Y, Doped LaGaO_3 perovskite type oxide as a new oxide ionic conductor.J.Am Chem.Soc[J].1994,116:3801
[11] 任引哲，郭崇峰，彭程，等．稀土氧化物的电导及在SOFC中的应用．化学研究．[J]2001，12(1)
[12] Ishihara T Matsuda.H,Takita Y.J.Am.Selected papers on automatic Power transmission
Ceram.Soc[J]. 1994.77:3801
[13] Stevenson.J.W, ArmstrongTR,Mccready .E,etal.J.Chemical analysis of matels and alloys Electrochem.Soc [J].1997,144(10): 3614
[14] 尧巍华，唐子龙，张中太，谭强强，等．LaGaO_3基固体电解质在SOFC中的应用硅酸盐学报．[J]2002，30(3)
[2] 沙其骞．SOFC燃料电池空气电极材料—La_(1-x)Sr_xMnO_3粉体的制备及性能．稀土[J]．1994，15(1)．
[3] 张传福，黎昌俊，曾德文，等．燃料电池及其结构材料．有色金属(冶炼部分)[J]．1998，3(47)
[4] 王永钤，赵志国，李立本，等．燃料电池固体电解质．洛阳师专学报[J]．2000，19(2)
[5] 梁广川，陈玉如，吴厚政，等．燃料电池固体氧化物电解质研究进展．硅酸盐通报[J]．1999．5．
[6] 杨浩，陈文涛．固体电解质研究的实验方法及原理．商都学坛[J]．1994，3(14)．
[7] 阎景旺，董永来，于春英，等．中温固体氧化物燃料电池阳极基底及负载型电解质薄膜的研制．无机材料学报[J]．2001．16(5)．
[8] 江义，李文钊，王世忠．La_(0.8)Sr_(0.2)MO_3／YSZ高温电极交流阻抗研究．化学进展[J]．1997，9(4)．
[9] 江义．固体氧化物燃料电池最新发展动态．电化学[J]1998，4(4)．
[10] Ishihara T, Matsuda H,Takita Y, Doped LaGaO_3 perovskite type oxide as a new oxide ionic conductor.J.Am Chem.Soc[J].1994,116:3801
[11] 任引哲，郭崇峰，彭程，等．稀土氧化物的电导及在SOFC中的应用．化学研究．[J]2001，12(1)
[12] Ishihara T Matsuda.H,Takita Y.J.Am.Selected papers on automatic Power transmission
Ceram.Soc[J]. 1994.77:3801
[13] Stevenson.J.W, ArmstrongTR,Mccready .E,etal.J.Chemical analysis of matels and alloys Electrochem.Soc [J].1997,144(10): 3614
[14] 尧巍华，唐子龙，张中太，谭强强，等．LaGaO_3基固体电解质在SOFC中的应用硅酸盐学报．[J]2002，30(3)
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |