Department of Materials, Imperial College, London, SW7 2AZ, UK.
Nanoscale. 2019 Oct 3;11(38):17746-17758. doi: 10.1039/c9nr06740j.
Nano-structured metal-ceramic materials have attracted attention to improve performance in energy conversion applications. However, they have poor long-term stability at elevated temperatures due to coarsening of the metal nanoparticles. In this work we show that this can be mitigated by a novel design of the nano-structure of Ni cermet fuel electrodes for solid oxide cells. The strategy is to create a dual porosity microstructure, without the use of fugitive pore-formers, with micron-size pores to facilitate gas transport and nanoscale pores to control nano-particle coarsening. This has been achieved using a continuous hydrothermal synthesis and two-stage heat treatments to produce electrodes with micron size agglomerates of nano-structured porous Ni-Yttria-Stabilised-Zirconia (YSZ). This unique hierarchical microstructure combines enhanced electrochemical reaction in the high activity (triple phase boundary density 11 μm-2) nanoscale regions with faster gas diffusion in the micron-sized pores. The electrodes are aged at 800 °C in humidified 5% H2-N2 for up to 600 h. The electrochemical reaction resistance is initially 0.17 Ω cm2 but later reaches a steady long-term value of 0.15 Ω cm2. 3-D reconstruction of the electrodes after 10 h and 100 h of ageing reveals an increase in YSZ network connectivity and TPB percolation. This improvement is well-correlated to the 3-D tomography parameters using a physical model adapted from mixed conducting SOC air electrodes, which is also supported, for the first time, by numerical simulations of the microstructural evolution. These also reveal that in the long term, nickel coarsening is inhibited by the nanoscale entanglement of Ni and YSZ in the hierarchical microstructure.
纳米结构金属陶瓷材料因其在能量转换应用中提高性能的潜力而受到关注。然而,由于金属纳米颗粒的粗化,它们在高温下的长期稳定性较差。在这项工作中,我们展示了一种用于固体氧化物电池的 Ni 金属陶瓷燃料电极的纳米结构的新颖设计可以缓解这个问题。该策略是创建一种具有双重孔隙率的微观结构,而不使用易挥发的造孔剂,具有微米级的孔来促进气体传输和纳米级的孔来控制纳米颗粒的粗化。这是通过连续水热合成和两阶段热处理来实现的,以生产具有微米尺寸的纳米结构多孔 Ni-氧化钇稳定氧化锆 (YSZ) 团聚体的电极。这种独特的分层微观结构结合了在高活性(三相边界密度 11 μm-2)纳米区域增强的电化学反应和在微米级孔中更快的气体扩散。电极在 800°C 下的湿 5% H2-N2 中老化长达 600 h。电化学反应电阻最初为 0.17 Ω cm2,但后来达到 0.15 Ω cm2 的稳定长期值。老化 10 h 和 100 h 后对电极进行的 3-D 重建显示出 YSZ 网络连通性和 TPB 渗流的增加。这种改进与使用从混合导电 SOC 空气电极改编的物理模型得出的 3-D 断层摄影术参数密切相关,这也是首次通过对微观结构演化的数值模拟得到支持。这些还表明,在长期内,纳米级 Ni 和 YSZ 的缠结抑制了镍的粗化。