Fine-Tuning of Air Electrode Microstructure and Its Composition as a Way to Enhance the Performance and Durability of Solid Oxide Electrolyzer - preliminary results

Anna Niemczyk, Stanisław Jagielski, Ryszard Kluczowski, Jakub Kupecki, Magdalena Kosiorek, Małgorzata Szczygieł
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Abstract

Among actions undertaken to reach a net-zero economy by 2050, implementation of the hydrogen technologies into various sectors e.g. energy and transport seems to be crucial. The significant increase of the installed capacity of electrolyzer in the last few years has been observed, which will accelerate in next decades to meet declared by many countries goals of their national hydrogen strategies. Nowadays, a dominant role on the electrolyze markets possess low temperature solution, namely, alkaline and PEM electrolyzes. However, due to higher efficiency – lower energy demand for hydrogen production, it is forecast that solid oxide electrolyzers (SOE) will take part of the market. The development of SOE, which are on the final R&D phase, is mainly focused on the extension of their lifespan and minimizing their manufacturing costs. The La 1-x Sr x CoO 3-δ (LSC) and La 1-x Sr x Co y Fe 1-y O 3-δ (LSCF) oxides due to their good catalytic activity and high mixed ionic-electronic conductivity are recognized as state-of-the-art air electrodes for SOC. However, Co-based perovskites are characterized by high thermal and chemical expansion, which might cause a mechanical mismatch with electrolyte, resulting in intensified SOC degradation. To mitigate mentioned issues different strategies have been proposed in the literature. Through the combined approach focused on modification of the bulk properties, simultaneously tailoring the microstructure of the electrodes and electrode/solid electrolyte interface, it is possible to overcome the kinetic limitations of operation at decreased temperatures. To maximize cell performance, and prevent the potential electrode degradation (i.e. its delamination) composite GDC-LSC/LSFC electrodes with gradual changes of the composition from electrolyte-electrode interphase to the electrode surface, were proposed. Furthermore, the impact of modification of electrode microstructure by an increase of its porosity and infiltration of the electrode surface with catalytically active oxides (e.g. Pr x O y ) was investigated. Fine-tuning of electrode porosity was achieved by the addition of the pore-forming agent, and the selection of its type (graphite or PMMA), amount, and size of its grains. Moreover, the work presents an approach to optimize the buffer layer, inter alia by its densifying, to mitigate Sr diffusion to the electrolyte and prevent air electrode delamination. The developed composite air electrodes were screen-printed (with an active area of 16 cm 2 ) on the fuel electrode-supported cell and evaluated in the SOE mode at the 650-750 °C temperature range. Tests included measurements of j-V dependences and EIS spectra (at different temperatures, current densities, and for different gas flow delivered at the air side of the cell). In order to assess the impact of the added amount and type of pore-forming agent on the microstructure of the electrode layer, as well as to investigate possible microstructural changes of the cell after testing SEM, SEM-EDS, and FIB-SEM analysis were performed. The proposed modification of the composition and microstructure resulted in higher current densities and reduced cell polarization compared to standard cells with LSC and LSCF as the air electrode. Acknowledgments The presented research was financially supported by: the National Centre for Research and Development, Poland, within project no. LIDER/1/0003/L-12/20/NCBR/2021 (research related to composite GDC-LSC/LSFC electrodes), and Ministry of Science and Higher Education through the statutory grant, within grant no. CPE.4000.001.2023 (research related to the improvement of the buffer layer-electrode interphase).
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空气电极结构及其组成的微调是提高固体氧化物电解槽性能和耐用性的一种途径——初步结果
在为到2050年实现净零经济而采取的行动中,在能源和交通等各个部门实施氢技术似乎至关重要。电解槽装机容量在过去几年中显著增加,并将在未来几十年加速增长,以实现许多国家宣布的国家氢战略目标。目前,在电解质市场上占据主导地位的是低温溶液,即碱性和PEM电解质。然而,由于更高的效率和更低的制氢能源需求,预计固体氧化物电解槽(SOE)将占据市场的一部分。SOE的开发处于最后的研发阶段,主要集中在延长其使用寿命和最小化其制造成本上。la1 -x Sr x CoO 3-δ (LSC)和la1 -x Sr x Co y Fe 1-y O 3-δ (LSCF)氧化物由于其良好的催化活性和高的混合离子电子电导率被认为是最先进的SOC空气电极。然而,钴基钙钛矿具有高热膨胀和化学膨胀的特点,这可能导致与电解质的机械失配,从而加剧SOC的降解。为了缓解上述问题,文献中提出了不同的策略。通过组合方法专注于本体性能的修改,同时定制电极和电极/固体电解质界面的微观结构,有可能克服在低温下操作的动力学限制。为了最大限度地提高电池性能,防止潜在的电极降解(即电极分层),提出了从电解质-电极界面到电极表面组成逐渐变化的GDC-LSC/LSFC复合电极。此外,还研究了通过增加电极孔隙率和电极表面渗透具有催化活性的氧化物(如Pr x O y)来修饰电极微观结构的影响。通过添加成孔剂、选择成孔剂的类型(石墨或PMMA)、颗粒的数量和尺寸,实现了电极孔隙度的微调。此外,该工作提出了一种优化缓冲层的方法,特别是通过其致密化,以减轻锶扩散到电解质并防止空气电极分层。所开发的复合空气电极被丝网印刷(活性面积为16 cm 2)在燃料电极支撑的电池上,并在650-750°C的温度范围内在SOE模式下进行评估。测试包括测量j-V依赖性和EIS光谱(在不同温度、电流密度和电池空气侧输送的不同气体流量下)。为了评估成孔剂的添加量和类型对电极层微观结构的影响,并探讨测试后电池可能发生的微观结构变化,我们进行了SEM- eds和FIB-SEM分析。与LSC和LSCF作为空气电极的标准电池相比,所提出的成分和微观结构的修改导致更高的电流密度和降低的电池极化。本研究由波兰国家研究与发展中心资助,项目编号为。LIDER/1/0003/L-12/20/NCBR/2021(与GDC-LSC/LSFC复合电极相关的研究),并通过科学和高等教育部的法定资助,在资助号内。CPE.4000.001.2023(缓冲层-电极界面改进相关研究)。
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