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可逆燃料电池—电解池氧电极复合改性研究

Study on Combined Modification of Oxygen Electrode for Reversible Solid Oxide Fuel Cell-electrolysis Cell

【作者】 范慧

【导师】 韩敏芳; Prabhakar Singh;

【作者基本信息】 中国矿业大学(北京) , 应用化学, 2014, 博士

【摘要】 固体氧化物燃料电池是一种可以直接将燃料的化学能转化为电能的电化学装置,固体氧化物电解池是固体氧化物燃料电池的逆过程,能够高温电解水/二氧化碳制氢气/一氧化碳。可逆电池将二者的功能合二为一。本论文主要进行了可逆电池的氧电极的复合改性研究。采用LSM((La0.8Sr0.2)0.95MnO3-δ),LSCF(La0.6Sr0.4Co0.2Fe0.8O3-δ)和SSC(Sm0.5Sr0.5CoO3-δ))氧电极材料。采用丝网印刷工艺制备的LSM和LSCF氧电极材料用于高温电解池和可逆电池,长期运行后,LSM与电解质YSZ(氧化钇稳定的氧化锆)发生剥离,YSZ与GDC(Gd0.1Ce0.9O2-δ)阻挡层剥离,导致电池性能衰减。浸渍工艺制备纳米LSM-YSZ,LSCF-YSZ和SSC-YSZ氧电极用于可逆电池,提高了氧电极的性能和催化活性。可逆循环测试或长期稳定性测试后,纳米离子发生团聚导致电池性能衰减。对SSC氧电极的研究发现氧电极SSC与YSZ分层,以及长期电解后氢电极Ni的团聚也是导致电池性能衰减的主要原因之一。最后,将纳米LSCF-YSZ氧电极用于H2O/CO2共电解,研究了共电解的影响因素和反应过程。综上,通过本论文研究为开发高活性和高稳定的氧电极材料奠定了基础。

【Abstract】 A solid oxide fuel cell (SOFC) is an electrochemical setup to convert chemical energy offuels into electric energy. A solid oxide electrolysis cell (SOEC) was reversibly operated as toSOFCs. H2/CO can be generated from H2O/CO2via an SOEC. A reversible cell integrated SOFCwith SOEC. In this study, LSM, LSCF and SSC oxygen electrodes are prepared for reversibleSOFCs. Electrochemical performance and stability of the oxygen electrodes for cells wereinvestigated, and degradation mechanism was demonstrated.LSM and LSCF electrodes prepared by screen printing were used for reversible SOFCs.After long-term steam electrolysis operation, SOEC deteriorated. Microstructure of post-test cellswas studied that delamination of LSM from YSZ and GDC from YSZ caused the deterioration.Furthermore, LSM-infiltrated YSZ oxygen electrode was prepared for reversible SOFC, so as toimprove the electrochemical performance and operational stability of the cell.Nano-sized LSM-YSZ, LSCF-YSZ, and SSC-YSZ oxygen electrodes were prepared for reversibleSOFCs by an infiltration process, with improved electrode performance and electro-catalyticactivity. Cell degradation in electrolysis mode is attributed to agglomeration of nano-particles,which has been observed during post-test SEM analysis. Agglomeration of infiltrated LSCFparticles is possibly responsible for the performance degradation of the cell. Rversible cells withSSC-YSZ oxygen electrodes degraded due to delamination of SSC-YSZ oxygen electrod fromYSZ electrolyte and coarsening of Ni particles. H2O/CO2co-electrolysis was investigated onLSCF-infiltrated YSZ oxygen electrode.In conclusion, this dissertation has established a solid foundation for development ofhigh-activity and high-stability oxygen electrodes.

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