基于锰铁掺杂的铬酸锶镧的燃料电池阳极复合材料研究
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摘要
固体氧化物燃料电池(SOFC)是一种全固态的发电装置,它具有高效率,低污染的优点,基于这些优点,对SOFC的研究达到了空前的热度。传统的SOFC以氧化钇稳定氧化锆(YSZ)为电解质、使用氢气(H_2)作为燃料,其阳极通常使用Ni/YSZ金属陶瓷材料,在H_2条件下它表现出卓越的性能。但是,H_2主要是通过电解水或裂解石油制备,造成SOFC燃料成本偏高,为了降低运行成本、推进SOFC的实用化,需要直接使用含碳燃料,但以Ni/YSZ为阳极的SOFC在对含碳燃料的测试中却出现了明显的性能衰退。这就迫使我们去寻找一种全新的阳极材料。钙钛矿氧化物凭借自己在氧化和还原气氛下突出的稳定性优势,作为SOFC阳极材料引起了广泛的关注。
研究发现,用碱土和过渡族元素分别对LaCrO_3的La位和Cr位进行掺杂能够有效地改善材料的电催化性能,使这种原本用于SOFC连接体的材料被成功改造为具有抗御碳沉积能力的阳极材料。其中,掺杂较为成功的材料是La_xSr_(1-x)Cr_yMn_(1-y)O_(3-δ)(LSCrM)和La_xSr_(1-x)Cr_yFe_(1-y)O_(3-δ)(LSCrFe),它们在还原气氛中表现出了良好的稳定性,但这两种材料的电导率都不够高、电催化能力也非常有限。本文的研究重点就是将具有高离子导电性的SDC,高电子导电性并具有阳极催化能力的Ni,Cu,Ag等掺入到LSCrM和LSCrFe中,形成复合阳极材料,以提升和改善其阳极的性能。以纯LSCrM为阳极,YSZ为电解质,(La,Sr)MnO_3(LSM)为阴极的SOFC在H_2条件下850oC的输出功率密度为230mW/cm~2。在同样的测试条件下,以浸渍SDC的LSCrM为阳极的SOFC输出性能达到了400mW/cm~2,如果将具有高催化性能的Ni和高离子电导率的SDC同时浸渍到LSCrM电极材料中,电池的性能达到1100mW/cm~2,这是迄今为止有关LSCrM报道的最高值。在对含碳燃料CH_4的测试中电池的输出性能提高的更为明显,由Ni和SDC浸渍的LSCrM阳极使SOFC的输出功率密度达到645mW/cm~2。与LSCrM一样,LSCrFe电极的掺杂也同样取得了显著的成效,以Ni和SDC浸渍LSCrFe为阳极的SOFC在H_2和CH4条件下的输出功率密度分别达到了783和214mW/cm~2(850oC)。
本文还对传统的机械混合和新的溶液浸渍复合阳极制备方法做了相应的对比,证明浸渍方法更为有效。在对浸渍Ni的钙钛矿电极进行6h的连续运行测试过程中性能衰退并不明显,并且在最终的电镜照片中也没有发现碳沉积。这表明,微量Ni催化剂的存在并不会引起明显碳沉积,因此只要有效控制Ni在电极中的含量,可以在不引起碳沉积的情况下极大的提升电极的催化性能。为了确保浸渍的纳米颗粒能够在电极内部分布得更加均匀,我们采取了真空浸渍的手段,并对常压浸渍和真空浸渍结果进行了对比。为了考察复合阳极中Ni的含量对其性能的影响,我们采用不同浓度的Ni(NO_3)_2溶液对电极进行浸渍处理,最终的测试结果表明电极的催化性能随Ni含量的增加而不断改善。
上述研究结果表明,在LSCrM和LSCrFe基础上制备的SOFC复合阳极材料具有很好的发展前景。
The Solid oxide fuel cell (SOFC) is an all solid energy conversion device with high efficiency and very low greenhouse emission. For this reason, different types of fuel cells are currently under development, and in most cases they use Y-doped ZrO_2 (YSZ) as the electrolyte, Ni/YSZ as the anode and hydrogen as the fuel. Although hydrogen is the most appropriate fuel for SOFC to achieve high peroformance, it can only be obtained through reforming of hydrocarbons, electrolysis or photo-electrolysis. Economically, it is ideal to use any hydrocarbons directly instead of being converted to hydrogen as the fuel for SOFC. Furthermore, the conventional Ni-based (Ni/YSZ) cermets anodes could produce excellent performance with hydrogen fuel at SOFC operating conditions, but, they degrade rapidly when operated in weakly humidified hydrocarbons. Thus, there is also considerable impetus to develop alternative materials to replace the Ni-cermet as the SOFC anode. Currently, perovskite oxides have been developed as Ni-free SOFC anodes due to their excellent stability both in an oxidizing and a reducing atmosphere.
Substitution of alkaline earth ions, transition elements into the A- and B-site of LaCrO_3, respectively, can be effectively carried out to improve the performance of the perovskite materials. La_xSr_(1-x)Cr_yMn_(1-y)O_(3-δ) (LSCrM) and La_xSr_(1-x)Cr_yFe_(1-y)O_(3-δ) (LSCrFe) are stable under redox cycling and are physically and chemically compatible with interconnect materials, but their conductivity is very limited with 18S/cm in air and 9S/cm in hydrogen at 850oC for LSCrM and 10S/cm in air and 0.5S/cm in hydrogen at 850oC for LSCrFe. This paper will focus on addition of the ionic conducing phase such as SDC and the electric conducing phase such as Ni, Cu, Ag increasing the reaction sites and enhancing the performance of the perovskite anode. The performance of the conventional electrolyte-supported cell LSCrM/YSZ/(La,Sr)MnO_3 while operating on hydrogen was modest with a maximum power density of 300mW/cm2 at 850oC, and the corresponding value for the cell with SDC-impregnated LSCrM anode was 400 mW/cm2 at 850oC. When Ni and SDC were introduced into the LSCrM anode together the value reached to 1100 mW/cm2 at 850oC at the same testing conditions, and the corresponding value for the cell while operating on methane with a maximum power density of 645mW/cm2 at 850oC. For Ni and SDC dipping LSCrFe anode, enhanced performance was 783 and 214mW/cm2 in hydrogen and methane at 850oC, respectively. In this paper, we compared mixed and wet impregnation and demonstrated the great potential of the wet impregnation method in the development of high performance and nano-structured electrodes with specific functions. There was no coking in the Ni-doping perovskite anode after testing in methane for about 6 hours indicating that the introduction of the metal Ni not only caused no coking but also enhanced the catalytic activity of the perovskite anode. In order to ensure the evenly distribution of the nanoparticles impregnated in the electrode, the entire process of the impregnation was in a vacuum. In this paper, we compared the atmospheric with vacuum impregnation showing the advantages and disadvantages of them. In order to investigate the contribution of Ni to the enhanced performance of the electrode, the perovskite anodes containing different amount of Ni content were fabricated and tested indicating the electrocatalytic activity of the composite anodes enhanced with the increasing of the Ni content.
These results above mentioned indicate that LSCrM- and LSCrFe-based are promising composite anode materials for SOFC.
研究发现,用碱土和过渡族元素分别对LaCrO_3的La位和Cr位进行掺杂能够有效地改善材料的电催化性能,使这种原本用于SOFC连接体的材料被成功改造为具有抗御碳沉积能力的阳极材料。其中,掺杂较为成功的材料是La_xSr_(1-x)Cr_yMn_(1-y)O_(3-δ)(LSCrM)和La_xSr_(1-x)Cr_yFe_(1-y)O_(3-δ)(LSCrFe),它们在还原气氛中表现出了良好的稳定性,但这两种材料的电导率都不够高、电催化能力也非常有限。本文的研究重点就是将具有高离子导电性的SDC,高电子导电性并具有阳极催化能力的Ni,Cu,Ag等掺入到LSCrM和LSCrFe中,形成复合阳极材料,以提升和改善其阳极的性能。以纯LSCrM为阳极,YSZ为电解质,(La,Sr)MnO_3(LSM)为阴极的SOFC在H_2条件下850oC的输出功率密度为230mW/cm~2。在同样的测试条件下,以浸渍SDC的LSCrM为阳极的SOFC输出性能达到了400mW/cm~2,如果将具有高催化性能的Ni和高离子电导率的SDC同时浸渍到LSCrM电极材料中,电池的性能达到1100mW/cm~2,这是迄今为止有关LSCrM报道的最高值。在对含碳燃料CH_4的测试中电池的输出性能提高的更为明显,由Ni和SDC浸渍的LSCrM阳极使SOFC的输出功率密度达到645mW/cm~2。与LSCrM一样,LSCrFe电极的掺杂也同样取得了显著的成效,以Ni和SDC浸渍LSCrFe为阳极的SOFC在H_2和CH4条件下的输出功率密度分别达到了783和214mW/cm~2(850oC)。
本文还对传统的机械混合和新的溶液浸渍复合阳极制备方法做了相应的对比,证明浸渍方法更为有效。在对浸渍Ni的钙钛矿电极进行6h的连续运行测试过程中性能衰退并不明显,并且在最终的电镜照片中也没有发现碳沉积。这表明,微量Ni催化剂的存在并不会引起明显碳沉积,因此只要有效控制Ni在电极中的含量,可以在不引起碳沉积的情况下极大的提升电极的催化性能。为了确保浸渍的纳米颗粒能够在电极内部分布得更加均匀,我们采取了真空浸渍的手段,并对常压浸渍和真空浸渍结果进行了对比。为了考察复合阳极中Ni的含量对其性能的影响,我们采用不同浓度的Ni(NO_3)_2溶液对电极进行浸渍处理,最终的测试结果表明电极的催化性能随Ni含量的增加而不断改善。
上述研究结果表明,在LSCrM和LSCrFe基础上制备的SOFC复合阳极材料具有很好的发展前景。
The Solid oxide fuel cell (SOFC) is an all solid energy conversion device with high efficiency and very low greenhouse emission. For this reason, different types of fuel cells are currently under development, and in most cases they use Y-doped ZrO_2 (YSZ) as the electrolyte, Ni/YSZ as the anode and hydrogen as the fuel. Although hydrogen is the most appropriate fuel for SOFC to achieve high peroformance, it can only be obtained through reforming of hydrocarbons, electrolysis or photo-electrolysis. Economically, it is ideal to use any hydrocarbons directly instead of being converted to hydrogen as the fuel for SOFC. Furthermore, the conventional Ni-based (Ni/YSZ) cermets anodes could produce excellent performance with hydrogen fuel at SOFC operating conditions, but, they degrade rapidly when operated in weakly humidified hydrocarbons. Thus, there is also considerable impetus to develop alternative materials to replace the Ni-cermet as the SOFC anode. Currently, perovskite oxides have been developed as Ni-free SOFC anodes due to their excellent stability both in an oxidizing and a reducing atmosphere.
Substitution of alkaline earth ions, transition elements into the A- and B-site of LaCrO_3, respectively, can be effectively carried out to improve the performance of the perovskite materials. La_xSr_(1-x)Cr_yMn_(1-y)O_(3-δ) (LSCrM) and La_xSr_(1-x)Cr_yFe_(1-y)O_(3-δ) (LSCrFe) are stable under redox cycling and are physically and chemically compatible with interconnect materials, but their conductivity is very limited with 18S/cm in air and 9S/cm in hydrogen at 850oC for LSCrM and 10S/cm in air and 0.5S/cm in hydrogen at 850oC for LSCrFe. This paper will focus on addition of the ionic conducing phase such as SDC and the electric conducing phase such as Ni, Cu, Ag increasing the reaction sites and enhancing the performance of the perovskite anode. The performance of the conventional electrolyte-supported cell LSCrM/YSZ/(La,Sr)MnO_3 while operating on hydrogen was modest with a maximum power density of 300mW/cm2 at 850oC, and the corresponding value for the cell with SDC-impregnated LSCrM anode was 400 mW/cm2 at 850oC. When Ni and SDC were introduced into the LSCrM anode together the value reached to 1100 mW/cm2 at 850oC at the same testing conditions, and the corresponding value for the cell while operating on methane with a maximum power density of 645mW/cm2 at 850oC. For Ni and SDC dipping LSCrFe anode, enhanced performance was 783 and 214mW/cm2 in hydrogen and methane at 850oC, respectively. In this paper, we compared mixed and wet impregnation and demonstrated the great potential of the wet impregnation method in the development of high performance and nano-structured electrodes with specific functions. There was no coking in the Ni-doping perovskite anode after testing in methane for about 6 hours indicating that the introduction of the metal Ni not only caused no coking but also enhanced the catalytic activity of the perovskite anode. In order to ensure the evenly distribution of the nanoparticles impregnated in the electrode, the entire process of the impregnation was in a vacuum. In this paper, we compared the atmospheric with vacuum impregnation showing the advantages and disadvantages of them. In order to investigate the contribution of Ni to the enhanced performance of the electrode, the perovskite anodes containing different amount of Ni content were fabricated and tested indicating the electrocatalytic activity of the composite anodes enhanced with the increasing of the Ni content.
These results above mentioned indicate that LSCrM- and LSCrFe-based are promising composite anode materials for SOFC.
引文
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52. J. Pe?a-Martínez, D. Marrero-López, J. C. Ruiz-Morales, B. E. Buergler, P. Nú?ez, L. J. Gauckler. SOFC Test Using Ba0.5Sr0.5Co0.8Fe0.2O3-δas Cathode on La0.9Sr0.1Ga0.8Mg0.2O2.85 Electrolyte. Solid State Ionics. 2006, 177:2143~2147
53. T. Shimonosono, Y. Hirata, Y. Ehira, S. Sameshima, T. Horita, H. Yokokawa. Electronic Conductivity Measurement of Sm- and La-Doped Ceria Ceramics by Hebb–Wagner Method. Solid State Ionics. 2004, 174:27~33
54. J. C. Ruiz-Morales, J. Canales-vázquez, J. Pe?a-Martínez, D. M. L?pez, P. Nú?ez. On the Simulaneous Use of La0.75Sr0.25Cr0.5Mn0.5O3-δas Both Anode and Cathode Material with Improved Microstructure in Solid Oxide Fuel Cells. Electrochimica. Acta. 2006, 52:278~284
55. S. P. Jiang. A Review of Wet Impregnation-An Alternative Method for the Fabrication of High Performance and Nano-Structured Electrodes of Solid Oxide Fuel Cells. MAT. SCI. ENG A-STRUCT. 2006, 418:199~210
56. B. Wei, Z. Lü, X. Q. Huang, M. L. Liu, K. F. Chen, W. H. Su. Enhanced Performance of a Single-Chamber Solid Oxide Fuel Cell with an SDC-Impregnated Cathode. J. Power Sources. 2007, 167:58~63
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59. H. P. He, J. M. Hill. Carbon Deposition on Ni/YSZ Composites Exposed to Humidified Methane. Appl. Catal. A-Gen. 2007, 317:284~292
60. S. P. Jiang, X. J. Chen, S. H. Chan, J. T. Kwok. GDC-Impregnated (La0.75Sr0.25)(Cr0.5Mn0.5)O3 Anodes for Direct Utilization in Solid Oxide Fuel Cells. J. Electrochem. SOC. 2006, 153:A850~A856
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62. N. Laosiripojana, W. Sangtongkitcharoen, S. Assabumrungrat. Catalytic Steam Reforming of Ethane and Propane over CeO2-Doped Ni/Al2O3 at SOFC Temperature: Improvement of Resistance Toward Carbon Formation by theRedox Property of Doping CeO2. Fuel. 2006, 85:323~332
63. X. J. Chen, Q. L. Liu, S. H. Chan, N. P. Brandon, K. A. Khor. High Performance Cathode-Supported SOFC with Perovskite Anode Operating in Weakly Humidified Hydrogen and Methane. Electrochem. Commun. 2007, 9:767~772
64. S. W. Tao, J. T. S. Irvine. Catalytic Properties of the Perovskite Oxide La0.75Sr0.25Cr0.5Fe0.5O3-δin Relation to Its Potential as a Solid Oxide Fuel Cell Anode Material. Chem. Mater. 2004, 16: 4116~4121
65. J. Liu, B. D. Madsen, Z. Q. Ji, S. A. Barnett. A Fuel-Flexible Ceramic-Based Anode for Solid Oxide Fuel Cells. Electrochem. Solid St. 2002, 5(6):A122~A124
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51. B. Huang, S. R. Wang, R. Z. Liu, X. F. Ye, H. W. Nie, X. F. Sun, T. L. Wen. Performance of La0.75Sr0.25Cr0.5Mn0.5O3-δPerovskite-Structure Anode Material atLanthanum Gallate Electrolyte for IT-SOFC Running on Ethanol Fuel. J. Power Sources. 2007, 167:39~46
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54. J. C. Ruiz-Morales, J. Canales-vázquez, J. Pe?a-Martínez, D. M. L?pez, P. Nú?ez. On the Simulaneous Use of La0.75Sr0.25Cr0.5Mn0.5O3-δas Both Anode and Cathode Material with Improved Microstructure in Solid Oxide Fuel Cells. Electrochimica. Acta. 2006, 52:278~284
55. S. P. Jiang. A Review of Wet Impregnation-An Alternative Method for the Fabrication of High Performance and Nano-Structured Electrodes of Solid Oxide Fuel Cells. MAT. SCI. ENG A-STRUCT. 2006, 418:199~210
56. B. Wei, Z. Lü, X. Q. Huang, M. L. Liu, K. F. Chen, W. H. Su. Enhanced Performance of a Single-Chamber Solid Oxide Fuel Cell with an SDC-Impregnated Cathode. J. Power Sources. 2007, 167:58~63
57. K F. Chen, Z. Lü, N. Ai, X. J. Chen, J. Y. Hu, X. Q. Huang, W. H. Su. Effect of SDC-Impregnated LSM Cathodes on the Performance of Anode-Supported YSZ Films for SOFCs. J. Power Sources. 2007, 167:84~89
58. S. W. Tao, J. T. S. Irvine, J. A. Kilner. An Efficient Solid Oxide Fuel Cell Based Upon Single-Phase Perovskite. Adv. Mater. 2005, 17:1734~1737
59. H. P. He, J. M. Hill. Carbon Deposition on Ni/YSZ Composites Exposed to Humidified Methane. Appl. Catal. A-Gen. 2007, 317:284~292
60. S. P. Jiang, X. J. Chen, S. H. Chan, J. T. Kwok. GDC-Impregnated (La0.75Sr0.25)(Cr0.5Mn0.5)O3 Anodes for Direct Utilization in Solid Oxide Fuel Cells. J. Electrochem. SOC. 2006, 153:A850~A856
61. N. Laosiripojana, S. Assabumrungrat. Catalytic Dry Reforming of Methane over High Surface Area Ceria. Appl. Catal. B-Environ. 2005, 60:107~116
62. N. Laosiripojana, W. Sangtongkitcharoen, S. Assabumrungrat. Catalytic Steam Reforming of Ethane and Propane over CeO2-Doped Ni/Al2O3 at SOFC Temperature: Improvement of Resistance Toward Carbon Formation by theRedox Property of Doping CeO2. Fuel. 2006, 85:323~332
63. X. J. Chen, Q. L. Liu, S. H. Chan, N. P. Brandon, K. A. Khor. High Performance Cathode-Supported SOFC with Perovskite Anode Operating in Weakly Humidified Hydrogen and Methane. Electrochem. Commun. 2007, 9:767~772
64. S. W. Tao, J. T. S. Irvine. Catalytic Properties of the Perovskite Oxide La0.75Sr0.25Cr0.5Fe0.5O3-δin Relation to Its Potential as a Solid Oxide Fuel Cell Anode Material. Chem. Mater. 2004, 16: 4116~4121
65. J. Liu, B. D. Madsen, Z. Q. Ji, S. A. Barnett. A Fuel-Flexible Ceramic-Based Anode for Solid Oxide Fuel Cells. Electrochem. Solid St. 2002, 5(6):A122~A124