金属复合纳米催化剂增强固体氧化物燃料电池阳极使用含烃燃料的性能和稳定性

Saad Waseem, Matthew Barre, Katarzyna Sabolsky, Richard Hart, Seunghyuck Hong, Edward Sabolsky
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摘要

将纳米催化剂材料应用于固体氧化物燃料电池(SOFC)电极以提高其性能和稳定性已经得到了广泛的研究。在电极结构中加入纳米催化剂可以通过增加三相边界(TPB)面积、提高氧化还原稳定性和改变烃类气体的反应动力学来提高SOFC的电化学性能,这些烃类气体会导致碳沉积导致阳极降解。在重整器上游作业的sofc需要对可能进入储层的任何碳氢化合物组分表现出良好的耐受性。典型的镍基金属陶瓷阳极在烃类流动下由于碳的积累而发生阳极失活。碳积聚并覆盖TPB区域,导致电化学性能差。较大的碳沉积会阻塞阳极微观结构中的孔隙,从而导致气体扩散问题。由于体积的变化,碳的积累也会对电极造成机械应力,从而导致电池的断裂和完全失效。本文研究了用纳米催化剂修饰镍基金属陶瓷阳极,促进其内部重整以防止结焦。研究了活性金属组分(如Co、Ge、Sn)和陶瓷转化促进剂(如ceo2、MgO)的添加。还研究了几种催化剂的多组分体系。通过专利的液相表面活性剂辅助工艺(使用各种儿茶酚表面活性剂),纳米催化剂均匀地掺入阳极微观结构中。通过改变表面活性剂和催化剂溶液的浓度来控制纳米颗粒的沉积负载密度和分布。通过扫描电子显微镜(SEM)成像、原子力显微镜(AFM)形貌分析和能量色散x射线光谱(EDS)化学表征表征纳米催化剂沉积。图1显示了氧化铈(ceo2)和氧化钴(CoO)在阳极结构内共沉积的纳米催化剂分布的SEM成像。观察到纳米级催化剂材料分布均匀。通过对称阳极测试完成SOFC纳米催化剂的加速评价,其中对称阳极电池在SOFC工作温度下受到碳氢化合物杂质的影响,并随着时间的推移进行电化学阻抗谱(EIS)表征。选择了最佳催化剂体系,并通过电流-电压-功率(I-V-P)和EIS评估完成了长期SOFC测试。尸体显微结构和化学表征也用于分析。在恶劣的环境和长期的测试中,电池在40%的ch4中持续50+ h, ceo2和CoO在阳极结构内均匀的纳米催化剂分布显示出50%以上的持续改善
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Metal Composite Nano-Catalyst Enhanced Solid Oxide Fuel Cell Anodes for Improved Performance and Stability with Hydrocarbon Containing Fuels
Implementation of nano-catalyst materials into solid oxide fuel cell (SOFC) electrodes to improve performance and stability has been widely studied. Addition of the nano-catalysts into an electrode structure serves to enhance the electrochemical performance of the SOFC by increasing the Triple Phase Boundary (TPB) area, improving redox stabilization, and modifying reaction kinetics of hydrocarbon gasses that cause anode degradation due to carbon deposition. SOFCs operating upstream of a reformer need to exhibit good tolerance to any hydrocarbon components that may make their way to the stack. Typical Ni-based cermet anodes suffer from anode deactivation due to carbon build up under hydrocarbon flows. Carbon builds up and covers the TPB area which results in poor electrochemical performance. Larger carbon deposits can block pores within the anode microstructure which leads to gas diffusion issues. Carbon buildup also causes mechanical stresses to the electrode due to volumetric changes which can lead to fracture and complete failure of the cell. This work studied nano-catalyst decoration of the Ni-based cermet anodes with catalysts that promote internal reforming to protect against coking. Addition of active metal components (such as Co, Ge, Sn), and ceramic reforming promoters (such as CeO 2 , MgO) were investigated. Multi-component systems with several catalysts were also examined. Uniform incorporation of nano-catalyst into the anode microstructure was achieved through a patented liquid phase surfactant assisted process (using various catechol surfactants). Deposition loading densities and distribution of nanoparticles was controlled by altering the surfactant and catalyst solution concentrations. Nano-catalyst depositions were characterized through Scanning Electron Microscope (SEM) for imaging, Atomic Force Microscopy (AFM) for topographical analysis, and Energy-Dispersive X-ray Spectroscopy (EDS) for chemical characterization. Figure 1 shows SEM imaging of nano catalyst distribution of cerium oxide (CeO 2 ) and cobalt oxide (CoO) co-deposition within an anode structure. A uniform distribution of nano-sized catalyst materials is observed. Accelerated evaluation of nano-catalysts for SOFCs was completed through symmetrical anode tests, where a symmetrical anode cell was subjected to hydrocarbon impurity at SOFC operating temperatures and electrochemical impedance spectroscopy (EIS) characterization was done over time. The best catalyst systems were down selected and long-term SOFC tests were completed with current-voltage-power (I-V-P) and EIS evaluation. Post-mortem microstructure and chemistry characterizations were also used in analysis. Uniform nano catalyst distribution of CeO 2 and CoO within the anode structure demonstrated greater than 50% sustained improvement in harsh environment, long-term tests where the cell was subjected to 40% CH 4 for 50+ h. Figure 1
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