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(Keynote) Releasing the Bubbles: Efficient Phase Separation in (Photo-)Electrochemical Devices in Microgravity Environment (主题演讲)释放气泡:微重力环境下光电电化学器件的高效相分离
Pub Date : 2023-08-28 DOI: 10.1149/ma2023-01562715mtgabs
Katharina Brinkert, Álvaro Romero-Calvo, Oemer Akay, Shaumica Saravanabavan, Eniola Sokalu
One of the major challenges human space exploration faces is the absence of buoyancy forces in orbit. Consequently, phase separation is severely hindered which impacts a large variety of space technologies including propellant management devices, heat transfer and life support systems e.g., during the production of oxygen and the recycling of carbon dioxide. Of particular interest are hereby (photo-)electrochemical (PEC) devices as they can produce essential chemicals such as oxygen and hydrogen in two set-ups: either, by coupling the electrochemical cell to external photovoltaic cells as currently utilized on the International Space Station or by direct utilization of sunlight in a monolithic device, where integrated semiconductor-electrocatalyst systems carry out the processes of light absorption, charge separation and catalysis in analogy to natural photosynthesis in one system. The latter device is particularly interesting for space applications due to present mass and volume constraints. Here, we discuss two combined approaches to overcome phase separation challenges in (photo-)electrolyzer systems in reduced gravitational environments: using the hydrogen evolution reaction (HER) as a model reaction, we combine nanostructured, hydrophilic electrocatalyst surfaces for efficient gas bubble desorption with magnetically-induced buoyancy to direct the produced hydrogen gas bubbles on specific trajectories away from the (photo-)electrode surface. (Photo-)current-voltage ( J-V ) profiles obtained in microgravity environments generated for 9.2 s at the Bremen Drop Tower show that our systems can operate with our two-fold approach near terrestrial efficiencies. Simulations of gas bubble trajectories accompany our experimental observations, allowing us to attribute the achieved phase separation in the PEC cells to the increased electrode wettability as well as the systematic use of diamagnetic and Lorentz forces.
人类太空探索面临的主要挑战之一是轨道上缺乏浮力。因此,相分离受到严重阻碍,影响到各种各样的空间技术,包括推进剂管理装置、传热和生命维持系统,例如在氧气生产和二氧化碳回收过程中。特别令人感兴趣的是(光电)电化学(PEC)装置,因为它们可以在两种设置中产生必需的化学物质,如氧和氢:要么是将电化学电池与外部光伏电池耦合,就像目前在国际空间站上使用的那样,要么是在一个单片装置中直接利用阳光,其中集成的半导体-电催化剂系统在一个系统中进行光吸收、电荷分离和催化过程,类似于自然光合作用。由于目前的质量和体积限制,后一种装置对于空间应用特别有趣。在这里,我们讨论了两种组合方法来克服在减少重力环境下(光)电解槽系统中相分离的挑战:使用析氢反应(HER)作为模型反应,我们结合了纳米结构,亲水电催化剂表面,用于有效的气泡解吸和磁诱导浮力,以指导产生的氢气气泡沿着特定的轨迹远离(光)电极表面。在不来梅落差塔(Bremen Drop Tower)获得的9.2 s微重力环境下的电流-电压(J-V)曲线表明,我们的系统可以以接近地面的双重效率运行。气泡轨迹的模拟伴随着我们的实验观察,使我们能够将PEC电池中实现的相分离归因于电极润湿性的增加以及抗磁性和洛伦兹力的系统使用。
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引用次数: 0
(Keynote) Electrochemistry on Mars – Two Years of MOXIE (Mars Oxygen ISRU Experiment) Operations Producing Oxygen on the Surface of the Red Planet (主题演讲)火星上的电化学-两年的MOXIE(火星氧气ISRU实验)操作在红色星球表面产生氧气
Pub Date : 2023-08-28 DOI: 10.1149/ma2023-01562739mtgabs
Jeffrey A. Hoffman
By the time of the 243rd ECS, NASA’s Mars2020 Perseverance rover will have spent over two Earth years on the surface of Mars, during which time the MOXIE experiment ( M ars OX ygen I SRU E xperiment) will have produced oxygen at night and in the day during both the annual maximum and minimum atmospheric density periods, as well as at many other times during the year. MOXIE is the first demonstration of the use of indigenous resources (ISRU = In Situ Resource Utilization) on the surface of another planet. This talk will explain how MOXIE works and will present a summary of what MOXIE has accomplished, how its performance on Mars has changed with time, and plans for the future. The paper will also present results from an optimization study of a human-scale MOXIE-type system capable of providing the oxidizer for a 6–person Mars Ascent Vehicle. As an experiment carried inside the rover, MOXIE had to satisfy many constraints that would not apply to an independent, full-scale system. Other potential oxygen-producing technologies should be compared to the optimized human-scale system results summarized in this paper rather than to a simple linear scaling of the mass, power consumption, and oxygen production rate of MOXIE.
到第243次ECS时,美国宇航局的火星2020毅力号火星车将在火星表面度过两个地球年以上的时间,在此期间,MOXIE实验(火星氧I SRU E实验)将在每年最大和最小大气密度期间的夜间和白天以及一年中的许多其他时间产生氧气。MOXIE是在另一个星球表面利用本地资源(ISRU =就地资源利用)的第一次示范。这次演讲将解释MOXIE是如何工作的,并将总结MOXIE所取得的成就,它在火星上的表现是如何随着时间的推移而变化的,以及未来的计划。本文还将介绍一项人类规模的moxie型系统的优化研究结果,该系统能够为6人火星上升飞行器提供氧化剂。作为一项在漫游车上进行的实验,MOXIE必须满足许多不适用于独立的全尺寸系统的限制。其他潜在的产氧技术应该与本文总结的优化的人类尺度系统结果进行比较,而不是简单地按MOXIE的质量、功耗和产氧速率进行线性缩放。
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引用次数: 0
A-Site Deficient Lst-Based Perovskite Fibers with Ni Exsolution for Reversible Solid Oxide Cells 可逆固体氧化物电池用含Ni外溶的缺a位lst基钙钛矿纤维
Pub Date : 2023-08-28 DOI: 10.1149/ma2023-0154218mtgabs
Jiaming Yang, Yueyue Sun, Lei Fu, Zhengrong Liu, Jun Zhou, Kai Wu
Reversible solid oxide cells (RSOCs) as new energy converting devices with superior conversion efficiency can operate in both fuel cell (FC) mode and electrolysis cell (EC) mode. However, the main challenges for fuel electrode materials are poor electrochemical performance and limited durability due to the sluggish hydrogen catalysis kinetics. Here, we demonstrate an advanced fiber-structured La x Sr x Ti 0.9 Ni 0.1 O 3-δ (LSTNx) architecture with a series of A-site deficiency (x=0.5, 0.45, and 0.4), which can be applied to reversible solid cells as a promising candidate of fuel electrode materials. LSTNx fibers decorated with Ni nanoparticles (NPs) were fabricated via electrospinning technique and in-situ exsolution method. A-site deficiency played a critical role in Ni exsolution and the morphology of LSTNx nanofibers. La 0.4 Sr 0.4 Ti 0.9 Ni 0.1 O 3-δ fibers with moderate A-site deficiency displayed homogeneous Ni NPs on the surface and excellent stability at 800℃ in pure H 2 . A single cell with LSTN0.4 fuel electrode (~40 μm) | GDC barrier layer (~0.5 μm) | SSZ electrolyte (~250 μm) | GDC barrier layer (~0.5 μm) | composite LSCF-GDC air electrode (~40 μm) exhibits maximum power density of 547.44 mW·cm -2 at 800℃ in wet H 2 and the current density of -1.351 A·cm -2 under the potential of 1.5 V in 50% H 2 O/H 2 atmosphere. The 5-cyclic long-term reversible tests of FC and EC modes were carried out under the potential of 0.5/1.5 V for 60 h, respectively. The current density degradation was approximately 0.67% in EC mode and 2.73% in FC mode after 5-cyclic reversible tests in LSTN0.4 single cells, suggesting a reliable fiber-structured architecture for RSOCs. Figure 1
可逆固体氧化物电池(rsoc)作为一种新型的能量转换器件,具有优异的转换效率,可以在燃料电池(FC)模式和电解电池(EC)模式下工作。然而,由于氢催化动力学缓慢,燃料电极材料的主要挑战是电化学性能差和耐用性有限。在这里,我们展示了一种先进的纤维结构La x Sr x Ti 0.9 Ni 0.1 O 3-δ (LSTNx)结构,具有一系列a位缺陷(x=0.5, 0.45和0.4),可以应用于可逆固体电池,作为有希望的候选燃料电极材料。采用静电纺丝技术和原位溶出法制备了镍纳米粒子修饰的LSTNx纤维。a位缺失对镍的析出和LSTNx纳米纤维的形貌起关键作用。中等a位缺陷的La 0.4 Sr 0.4 Ti 0.9 Ni 0.1 O 3-δ纤维在表面表现出均匀的Ni NPs,在800℃纯h2中具有优异的稳定性。采用LSTN0.4燃料电极(~40 μm)、| GDC阻挡层(~0.5 μm)、| SSZ电解质(~250 μm)、| GDC阻挡层(~0.5 μm)、|复合LSCF-GDC空气电极(~40 μm)的单电池在800℃湿h2条件下的最大功率密度为547.44 mW·cm -2,在50% h2o / h2气氛下1.5 V电位下的电流密度为-1.351 A·cm -2。在0.5/1.5 V电势下分别进行FC和EC模式的5循环长期可逆试验,持续60 h。在LSTN0.4单细胞中进行5循环可逆测试后,在EC模式下电流密度下降约0.67%,在FC模式下电流密度下降约2.73%,表明rsoc具有可靠的纤维结构结构。图1
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引用次数: 0
(Invited) Current Status of SOFC Deployment and Technology Developments in Korea (特邀)韩国SOFC部署和技术发展现状
Pub Date : 2023-08-28 DOI: 10.1149/ma2023-01546mtgabs
Rak-Hyun Song
In Korea, the supply of stationary fuel cells for power generation is being promoted by the mandatory RPS program. The deployment of fuel cells in Korea began in 2012. Currently, fuel cells of about 880 MW have been supplied. Among them, the amount of SOFC system is about 220 MW, and the SOFC installation started in 2014. About 40 MW in 2021 and 50 MW in 2022 were installed. The deployment of residential SOFCs has just begun, and a small number of systems have been deployed. In Korea, fuel cell deployment is accelerated by the mandatory supply amount allocated to power generation companies by the RPS policy, and in addition, the clean energy supply promotion regulation granted to public buildings partially contributes to fuel cell supply. Several Korean companies have developed the SOFC and SOEC technologies under the national program, and major projects are the development of a 200 kW SOFC and a 20 kW SOEC systems. The 2~8kW class SOFC products have been developed already and are in deployment. In Korea, SOEC demonstration is being also promoted to store electricity generated from renewable energy, and about 1.5MW SOEC is scheduled to be demonstrated by 2024. The Korean government enacted the Hydrogen Law in 2019, and under this law, development and deployment of hydrogen and fuel cell-related technologies are in progress. In addition, a hydrogen roadmap was established as an implementation plan to encourage achievement of the deployment targets. In this talk, the achievements of the SOFC R&D and deployment, and national hydrogen roadmap in Korea are introduced in more detail.
在韩国,固定式燃料电池的供应正在通过强制性RPS计划得到推进。韩国从2012年开始使用燃料电池。目前,已提供约880兆瓦的燃料电池。其中SOFC系统容量约220兆瓦,SOFC安装于2014年启动。2021年安装了约40兆瓦,2022年安装了50兆瓦。住宅sofc的部署才刚刚开始,已经部署了少量系统。在韩国,燃料电池的普及得益于RPS政策对发电企业的强制供应额,再加上公共建筑的清洁能源供应促进规定也起到了一定的促进作用。韩国的一些企业已经根据国家计划开发了SOFC和SOEC技术,主要项目是开发200千瓦SOFC和20千瓦SOEC系统。2~8kW级的SOFC产品已经开发并正在部署中。韩国也在推进储存可再生能源发电的SOEC示范,计划到2024年为止示范1.5兆瓦左右的SOEC。韩国政府于2019年制定了《氢法》,根据该法律,氢和燃料电池相关技术的开发和部署正在进行中。此外,还制定了氢路线图作为实施计划,以鼓励实现部署目标。在这次演讲中,详细介绍了韩国在SOFC研发和部署方面取得的成就,以及韩国的国家氢路线图。
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引用次数: 0
La1.5Sr1.5Mn1.5Ni0.5O7 ±δ Vs La1.5Sr1.5Co1.5Ni0.5O7 ±δ: Exsolved Materials as Anodic Layers for Direct Biogas-Fueled SOFC La1.5Sr1.5Mn1.5Ni0.5O7±δ Vs La1.5Sr1.5Co1.5Ni0.5O7±δ:作为直接沼气燃料SOFC阳极层的外溶材料
Pub Date : 2023-08-28 DOI: 10.1149/ma2023-0154174mtgabs
Sebastian Vecino-Mantilla, Massimiliano Lo Faro, Gaetano Squadrito
Currently, one of the main problems in commercial SOFC systems fueled directly with hydrocarbon compounds, such as biogas, is the high risk of blocking the active phase on the anode side ( e.g. Ni-YSZ ) due to carbon formation/deposition during the conversion of fuel into power energy. This issue causes a lowering in the overall performance and durability of the cell. Therefore, to overcome this deactivation mechanism, it was successfully demonstrated that an additional anodic active layer in commercial SOFC using materials based on exsoluted perovskites could be an interesting and viable alternative. This asseveration is based on the fact that using this kind of material is possible to get heterogeneous surface systems with highly stable and electrocatalytically active embedded nanoparticles uniformly distributed on the surface with a high carbon coking tolerance in a hydrocarbon fuel atmosphere. This study aimed to evaluate and compare the electrocatalytic behaviour of two new catalytic materials with Ni exsolution for direct dry biogas-fueled SOFC. The starting materials were Ruddlesden-Popper-type based on a nickel manganite (La 1.5 Sr 1.5 Mn 1.5 Ni 0.5 O 7±δ or LSMN ) and nickel cobaltite (La 1.5 Sr 1.5 Co 1.5 Ni 0.5 O 7±δ or LSCN ). Both materials have been synthesized by the Pechini method using stoichiometric amounts of precursors as nitrates. Once the respective gels have been formed, they were treated in the air at two dwell temperatures, 300°C for 2 h and 500°C for 3 h, to ensure the total elimination of the organic compounds. Finally, the resulting powders were treated in air at 1300°C for 12h and then, physicochemically characterized. For the electrochemical characterization, the as-treated powders were mixed individually with Gd 0.1 Ce 0.9 O 2 ( CGO ) in a weight ratio of 70:30 using a ball milling for 6h. Finally, to get the slurry for the coating layer, each mixture ( LSMN+CGO and LSCN+CGO ) was ground for an additional 2h in the presence of 8 wt % of triethanolamine, 2 wt % polyvinyl butyral resin (BUTVAR B-98) and 2-propanol. Commercial button SOFC cells by InDEC® (anode-supported cell Ni-YSZ/YSZ/LSM) were painted on the anode side getting an active area of 2 cm 2 . The experiments were carried out at 800°C with pre-conditioning using diluted H 2 and then, with simulated dry biogas. A Biologic tool was used as a device for the electrochemical measurements. The purpose of this communication is to present the results of experiments with two button cells derived from the same large area commercial cell (anode supporting cell) coated with the two electrocatalysts developed in this work. The electrochemical test carried out for more than 200 h demonstrated that this external functional layer on the anode side contributes to getting a stable potential within the whole working time at the selected galvanostatic conditions (500 mA cm −2 ). By comparing the results of these two tests, the exsolved LSCN layer showed better perfomances, be
目前,直接以碳氢化合物(如沼气)为燃料的商用SOFC系统的主要问题之一是,在将燃料转化为电能的过程中,由于碳的形成/沉积,极有可能阻塞阳极侧的活性相(如Ni-YSZ)。这个问题会降低电池的整体性能和耐用性。因此,为了克服这种失活机制,成功地证明了在商用SOFC中使用基于外溶钙钛矿的材料的额外阳极活性层可能是一种有趣且可行的替代方案。这一结论是基于这样一个事实,即使用这种材料可以得到具有高稳定性和电催化活性的嵌入纳米颗粒的非均相表面体系,这些纳米颗粒在碳氢燃料气氛中均匀分布在表面上,并且具有高的碳焦化耐受性。本研究旨在评价和比较两种新型催化材料与Ni溶出液对直接干燥沼气燃料SOFC的电催化性能。起始材料为ruddlesden - popper型镍锰矿(La 1.5 Sr 1.5 Mn 1.5 Ni 0.5 O 7±δ或LSMN)和钴酸镍(La 1.5 Sr 1.5 Co 1.5 Ni 0.5 O 7±δ或LSCN)。这两种材料都是用化学计量量的前体作为硝酸盐通过Pechini方法合成的。一旦凝胶形成,它们将在空气中以两种停留温度(300°C 2小时和500°C 3小时)进行处理,以确保有机化合物的完全消除。最后,将得到的粉末在1300℃的空气中处理12h,然后进行物理化学表征。为了进行电化学表征,将处理后的粉末分别与Gd 0.1 Ce 0.9 o2 (CGO)以70:30的质量比混合,球磨6h。最后,为了得到用于涂层的浆料,每种混合物(LSMN+CGO和LSCN+CGO)在8wt %的三乙醇胺、2wt %的聚乙烯醇丁醛树脂(BUTVAR B-98)和2-丙醇的存在下再研磨2h。由InDEC®(阳极支撑电池Ni-YSZ/YSZ/LSM)制成的商用纽扣式SOFC电池被涂在阳极一侧,得到2平方厘米的有效面积。实验在800°C下进行,用稀释的h2预处理,然后用模拟的干燥沼气。采用生物工具作为电化学测量装置。本次交流的目的是展示两个纽扣电池的实验结果,这些纽扣电池来自于相同的大面积商业电池(阳极支撑电池),并涂有本工作中开发的两种电催化剂。200多小时的电化学测试表明,在选定的恒流条件下(500 mA cm−2),阳极侧的外部功能层有助于在整个工作时间内获得稳定的电位。通过比较这两种测试的结果,发现外溶的LSCN层表现出更好的性能,这是因为b位掺杂了Co而不是Mn,从而增强了晶体结构内的o2 -输运。最后,反应后表征显示,在两种情况下,碳物质都是最小的/零的,这表明,在商业SOFC中直接使用碳氢燃料造成的传统风险可以通过这种方法得到抑制,这将导致我们考虑在下一个层次或进一步的电化学应用中使用这种类型的材料。作者承认该项目名为“固体氧化物燃料电池中生物燃料的直接利用,用于可持续和分散的电力生产和供热(DIRECTBIOPOWER)”。资助协议编号:2017FCFYHK。作者感谢意大利生态转型部(MiTE)通过AdP“Piano Operativo di Ricerca (POR) sull'idrogeno verde图1”资助本研究
{"title":"La<sub>1.5</sub>Sr<sub>1.5</sub>Mn<sub>1.5</sub>Ni<sub>0.5</sub>O<sub>7</sub> <sub>±δ</sub> Vs La<sub>1.5</sub>Sr<sub>1.5</sub>Co<sub>1.5</sub>Ni<sub>0.5</sub>O<sub>7</sub> <sub>±δ</sub>: Exsolved Materials as Anodic Layers for Direct Biogas-Fueled SOFC","authors":"Sebastian Vecino-Mantilla, Massimiliano Lo Faro, Gaetano Squadrito","doi":"10.1149/ma2023-0154174mtgabs","DOIUrl":"https://doi.org/10.1149/ma2023-0154174mtgabs","url":null,"abstract":"Currently, one of the main problems in commercial SOFC systems fueled directly with hydrocarbon compounds, such as biogas, is the high risk of blocking the active phase on the anode side ( e.g. Ni-YSZ ) due to carbon formation/deposition during the conversion of fuel into power energy. This issue causes a lowering in the overall performance and durability of the cell. Therefore, to overcome this deactivation mechanism, it was successfully demonstrated that an additional anodic active layer in commercial SOFC using materials based on exsoluted perovskites could be an interesting and viable alternative. This asseveration is based on the fact that using this kind of material is possible to get heterogeneous surface systems with highly stable and electrocatalytically active embedded nanoparticles uniformly distributed on the surface with a high carbon coking tolerance in a hydrocarbon fuel atmosphere. This study aimed to evaluate and compare the electrocatalytic behaviour of two new catalytic materials with Ni exsolution for direct dry biogas-fueled SOFC. The starting materials were Ruddlesden-Popper-type based on a nickel manganite (La 1.5 Sr 1.5 Mn 1.5 Ni 0.5 O 7±δ or LSMN ) and nickel cobaltite (La 1.5 Sr 1.5 Co 1.5 Ni 0.5 O 7±δ or LSCN ). Both materials have been synthesized by the Pechini method using stoichiometric amounts of precursors as nitrates. Once the respective gels have been formed, they were treated in the air at two dwell temperatures, 300°C for 2 h and 500°C for 3 h, to ensure the total elimination of the organic compounds. Finally, the resulting powders were treated in air at 1300°C for 12h and then, physicochemically characterized. For the electrochemical characterization, the as-treated powders were mixed individually with Gd 0.1 Ce 0.9 O 2 ( CGO ) in a weight ratio of 70:30 using a ball milling for 6h. Finally, to get the slurry for the coating layer, each mixture ( LSMN+CGO and LSCN+CGO ) was ground for an additional 2h in the presence of 8 wt % of triethanolamine, 2 wt % polyvinyl butyral resin (BUTVAR B-98) and 2-propanol. Commercial button SOFC cells by InDEC® (anode-supported cell Ni-YSZ/YSZ/LSM) were painted on the anode side getting an active area of 2 cm 2 . The experiments were carried out at 800°C with pre-conditioning using diluted H 2 and then, with simulated dry biogas. A Biologic tool was used as a device for the electrochemical measurements. The purpose of this communication is to present the results of experiments with two button cells derived from the same large area commercial cell (anode supporting cell) coated with the two electrocatalysts developed in this work. The electrochemical test carried out for more than 200 h demonstrated that this external functional layer on the anode side contributes to getting a stable potential within the whole working time at the selected galvanostatic conditions (500 mA cm −2 ). By comparing the results of these two tests, the exsolved LSCN layer showed better perfomances, be","PeriodicalId":11461,"journal":{"name":"ECS Meeting Abstracts","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135087866","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Fine-Tuning of Air Electrode Microstructure and Its Composition as a Way to Enhance the Performance and Durability of Solid Oxide Electrolyzer - preliminary results 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
Pub Date : 2023-08-28 DOI: 10.1149/ma2023-0154205mtgabs
Anna Niemczyk, Stanisław Jagielski, Ryszard Kluczowski, Jakub Kupecki, Magdalena Kosiorek, Małgorzata Szczygieł
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 th
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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引用次数: 0
Spatially Heterogeneous Chemistry Observed using NIRTI on SOFC Anodes 利用NIRTI在SOFC阳极上观察空间非均相化学
Pub Date : 2023-08-28 DOI: 10.1149/ma2023-0154264mtgabs
Elias D Pomeroy, Daniel Steinhurst, Stanislav Tsoi, John David Kirtley, Bryan Eigenbrodt, Jeffrey Owrutsky, William A Maza, Robert A. Walker
Carbon formation remains the primary degradation mechanism for solid oxide fuel cells (SOFCs) operating on carbonaceous fuels. The mechanisms for the remediation of carbon (C) induced degradation via electrochemical gasification and reforming using O 2(g) and H 2 O (g) was studied using Near Infrared Thermal Imaging (NIRTI), Fourier Transform Infrared Emission Spectroscopy (FTIRES), chronoamperometry/chronopotentiometry (CA/CP), and mass spectrometry (MS). Carbon removal follows a stepwise mechanism, first oxidizing surface carbon to CO (g) , and subsequently to CO 2(g) . CO (g) oxidation requires a catalytic surface to form CO 2 which plays a key role in removing C via the reverse Boudouard chemistry. NIRTI reveals spatially heterogenous chemistry and suggests a specific role of surface oxygen species. These species form from dissociative adsorption and non-faradaic oxide flux through the electrolyte, as well as O 2 transport limited processes occurring due to high O 2 utilization. C removal from electrochemical oxidation and steam spatially homogeneous compared to O 2 , due in part to the respective active surface species, and their respective transport limitations. Under O 2 C removal is appears incomplete, despite electrochemical results. These experiments clarify the mechanisms responsible for remediation of C on SOFC anodes and highlight the need of spatially resolved techniques to study SOFCs under operating conditions.
对于使用含碳燃料的固体氧化物燃料电池(sofc)来说,碳形成仍然是主要的降解机制。采用近红外热成像(NIRTI)、傅里叶变换红外发射光谱(FTIRES)、时间电流/时间电位测定(CA/CP)和质谱(MS)研究了o2 (g)和h2o (g)电化学气化和重整对碳(C)诱导降解的修复机制。碳的去除遵循一个循序渐进的机制,首先将表面碳氧化为CO (g),然后氧化为CO 2(g)。CO (g)氧化需要一个催化表面来形成CO 2, CO 2在通过反向Boudouard化学去除C中起着关键作用。NIRTI揭示了空间上的非均相化学,并表明了表面氧的特定作用。这些物种形成于解离吸附和通过电解质的非法拉第氧化物通量,以及由于高o2利用率而发生的o2运输限制过程。与o2相比,电化学氧化和蒸汽对C的去除在空间上是均匀的,部分原因在于它们各自的活性表面物质,以及它们各自的传输限制。在o2 - C的去除下,尽管有电化学结果,但它似乎不完全。这些实验阐明了SOFC阳极上C的修复机制,并强调了在操作条件下研究SOFC的空间分辨技术的必要性。
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引用次数: 0
Automatic Data Curation and Analysis Pipeline for Electrochemical Impedance Spectroscopy Measurements Conducted on Solid Oxide Cell Stacks 在固体氧化物电池堆上进行的电化学阻抗光谱测量的自动数据管理和分析管道
Pub Date : 2023-08-28 DOI: 10.1149/ma2023-015460mtgabs
Christian Frederik Mänken, Dominik Schäfer, Rudiger-A Eichel, Felix Kunz
Abstract To better understand degradation in electrochemical converters and helping to correlate certain phenomena with specific operating conditions, machine learning (ML) methods are increasingly being applied. Success has already been achieved in the field of degradation analysis and prediction of capacity of lithium ion batteries 1 , for instance. In terms of Solid Oxide Cell (SOC) stacks ML methods have been applied mainly with the aim of identification of faulty operation modes and degradation related fault diagnosis 2 . ML approaches usually require a considerable amount of real training data, when used for forecasting models. A data consolidation and curation strategy was developed with the aim of processing the historic long-term test bench data of SOCs collected by Forschungszentrum Jülich over the past years. In comparison to other datasets developed in this field 3 , the one presented in this work contains SOC stack tests in fuel cell operation with significantly longer operating times under load. A compilation of the sample experiments and the consolidation into a hierarchical data format are presented. Further, an essential part of the strategy is the automatic curation and analysis of electrochemical impedance spectroscopy (EIS) measurements, using a specifically developed procedure in Python. The varying quality of measurements from past years, as well as recurring artefacts such as parasitic inductances, can be addressed in this way. Additional distribution of relaxation times (DRT) deconvolutions and equivalent circuit modelling (ECM) are performed, as part of the procedure to automatically retrieve feature values from measurements (cf. Fig. 1). The novel dataset, which to the authors’ knowledge includes some of the longest SOC stack tests available, serves as the basis for several evaluations. In addition to classification and clustering work to derive degradation patterns, in particular based on the EIS data, another focus is on the development of forecasting models. The current work is primarily concerned with long short-term memory (LSTM), as well as regression models that make use of both the time series data and the characterisation measurements, such as EIS. Acknowledgement The authors would like to thank their colleagues at Forschungszentrum Jülich GmbH for their great support and the Helmholtz Society as well as the German Federal Ministry of Education and Research for financing these activities as part of the WirLebenSOFC project (03SF0622B). References 1: Jones, P.K., Stimming, U. & Lee, A.A. Impedance-based forecasting of lithium-ion battery performance amid uneven usage. Nature Communications 13, 4806 (2022). 2: B. Yang et al. Solid oxide fuel cell systems fault diagnosis: Critical summarization, classification, and perspectives. Journal of Energy Storage 34 , 102153 (2021). 3: A.K. Padinjarethil, S. Pollok & A. Hagen. Degradation studies using machine learning on novel solid oxide cell database. Fuel Cells
为了更好地理解电化学转化器中的降解,并帮助将某些现象与特定的操作条件联系起来,机器学习(ML)方法正越来越多地得到应用。例如,在锂离子电池的退化分析和容量预测领域已经取得了成功。对于固体氧化物电池(SOC)堆栈,ML方法主要用于故障运行模式的识别和与退化相关的故障诊断2。当用于预测模型时,机器学习方法通常需要大量的真实训练数据。为了处理Forschungszentrum j lich在过去几年中收集的soc的历史长期试验台数据,制定了数据整合和管理策略。与该领域开发的其他数据集相比,本工作中提供的数据集包含燃料电池运行中的SOC堆栈测试,在负载下运行时间要长得多。给出了样本实验的汇编和分层数据格式的整合。此外,该策略的一个重要部分是电化学阻抗谱(EIS)测量的自动管理和分析,使用Python中专门开发的程序。过去几年测量质量的变化,以及寄生电感等反复出现的人为因素,都可以通过这种方式解决。执行额外的松弛时间分布(DRT)反卷积和等效电路建模(ECM),作为自动从测量中检索特征值的过程的一部分(参见图1)。据作者所知,新数据集包括一些最长的SOC堆栈测试,可作为若干评估的基础。除了分类和聚类工作,特别是根据环境信息系统数据得出退化模式外,另一个重点是发展预测模式。目前的工作主要关注长短期记忆(LSTM),以及利用时间序列数据和特征测量(如EIS)的回归模型。作者要感谢他们在Forschungszentrum j lich GmbH的同事们的大力支持,感谢亥姆霍兹学会以及德国联邦教育和研究部为这些活动提供资金,作为WirLebenSOFC项目(03SF0622B)的一部分。参考文献1:Jones, p.k., stiming, U. &;李,A.A.。基于阻抗的锂离子电池在不均匀使用中的性能预测。自然通讯13,4806(2022)。2: B. Yang等。固体氧化物燃料电池系统故障诊断:关键总结,分类和观点。储能学报,34(2)(2021)。3: A.K. Padinjarethil, S. Pollok &答:哈根。基于机器学习的新型固体氧化物电池数据库降解研究。燃料电池21,566-576(2021)。图说明:图1:EIS数据策展管道及以EIS测量为例的策展结果流程图。图1
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引用次数: 0
Electrochemical Deposition of Nanocatalysts on an Oxide Scaffold Enhances the Activity of Oxygen Reduction 纳米催化剂在氧化物支架上的电化学沉积提高了氧还原活性
Pub Date : 2023-08-28 DOI: 10.1149/ma2023-0154190mtgabs
Seongwoo Nam, Jinwook Kim, Hyunseung Kim, SungHyun Jeon, Sejong Ahn, Yoonseok Choi, Beom-Kyeong Park, WooChul Jung
Solid oxide fuel cells (SOFCs) are devices that directly convert the chemical energy of hydrogen and oxygen into electrical energy, and are attracting attention for their high efficiency and eco-friendliness. Since the recent research trend is to lower the operating temperature of the device, there is a considerable demand for a way to effectively introduce a catalyst to overcome the poor electrochemical activity of the most commercially available lanthanum strontium manganite–yttria-stabilized zirconia (LSM-YSZ) composite electrode. Praseodymium oxide (PrO x ) is an excellent catalyst for the ORR and has also been applied to LSM-YSZ electrodes via infiltration, the most widely used catalyst fabrication method. However, this previously well-established method still experiences time-consuming and energy-intensive limitations; therefore, other catalyst fabrication approaches are required. Cathodic electrochemical deposition (CELD) is chosen as a central strategy to decorate the PrO x catalyst which strongly empowers the exclusive ORR activity of the LSM-YSZ electrode. CELD is an excellent catalyst fabrication method that combines electroplating and chemical precipitation, and is simple, fast, cost-effective, and capable of deposition at room temperature and ambient pressure. Herein, we present an electrochemical deposition method that fabricating a PrO x overlayer significantly improves the catalytic activity of composite electrodes with only a short process of less than 4 min, even in an ambient environment. Moreover, it does not require additional processes such as heat treatment. The PrO x -coated electrode exhibits a decrease in initial polarization resistance compared to the bare, and maintained an oxygen reduction reaction characteristic by more than 10 times even after about 400 hours of operation at 650 °C. Transmission line model analysis with impedance spectra describes how PrO x improves the reactivity of the oxygen reduction reaction of composite electrodes. Finally, we demonstrate that a two-element material, (Pr, Ce)O x , was electrochemically deposited. Electrochemical deposition considerably improves the catalytic properties of the cathode via a concise and straightforward process.
固体氧化物燃料电池(SOFCs)是将氢和氧的化学能直接转化为电能的装置,因其高效率和环保性而备受关注。由于最近的研究趋势是降低器件的工作温度,因此迫切需要一种有效引入催化剂的方法来克服市面上最常见的镧锶锰钇稳定氧化锆(LSM-YSZ)复合电极电化学活性差的问题。氧化镨(PrO x)是一种优良的ORR催化剂,也被应用于LSM-YSZ电极上,这是最广泛使用的催化剂制造方法。然而,这种先前建立的方法仍然存在耗时和能量密集的局限性;因此,需要其他的催化剂制造方法。选择阴极电化学沉积(CELD)作为装饰PrO x催化剂的核心策略,这有力地增强了LSM-YSZ电极的排他ORR活性。CELD是一种优秀的催化剂制造方法,结合了电镀和化学沉淀,简单,快速,成本效益高,能够在室温和常压下沉积。在此,我们提出了一种电化学沉积方法,即使在环境中,也只需不到4分钟的短过程,就可以显著提高复合电极的催化活性。此外,它不需要额外的工艺,如热处理。与裸电极相比,PrO x涂层电极的初始极化电阻降低,即使在650℃下工作约400小时后,其氧还原反应特性仍保持在10倍以上。阻抗谱传输线模型分析描述了PrO x如何提高复合电极的氧还原反应活性。最后,我们证明了电化学沉积了一种双元素材料(Pr, Ce)O x。电化学沉积通过一个简洁直接的过程大大提高了阴极的催化性能。
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引用次数: 0
(Invited) Leveraging Magnetohydrodynamic Mechanisms for Stable and Efficient Microgravity Electrolysis (特邀)利用磁流体动力学机制实现稳定高效的微重力电解
Pub Date : 2023-08-28 DOI: 10.1149/ma2023-01562718mtgabs
Álvaro Romero-Calvo, Katharina Brinkert
Water electrolysis is the fundamental chemical process for oxygen and hydrogen production in space. It is widely employed in modern environmental control and life support systems, propulsion technologies, and high-density energy storage devices. Furthermore, future interplanetary missions are likely to employ water as a commodity acquired and processed by In Situ Resource Utilization (ISRU) methodologies to produce propellants, thereby reducing vehicle launch mass. The absence of buoyancy results in major technical challenges for the operation of electrolytic cells in low gravity. The need to detach and collect oxygen and hydrogen bubbles has been traditionally addressed by means of forced water recirculation loops. However, this leads to complex, inefficient, and unreliable liquid management devices composed of multiple elements and moving parts. Two distinct magnetohydrodynamic (MHD) mechanisms may instead be employed to induce phase separation: diamagnetic, and Lorentz forces. The former arises in the presence of strong, inhomogeneous magnetic fields and results in a magnetic buoyancy effect. The latter is a consequence of the imposition of a magnetic field to the current generated between two electrodes. Both approaches can potentially lead to a new generation of electrolytic cells with minimum or no moving parts, hence enabling the human deep space operations with minimum mass and power penalties. Dedicated microgravity experiments are required to study these novel magnetically enhanced electrolysis concepts. This presentation introduces the fundamentals of both methods and discusses the experimental design and results from several experimental campaigns at ZARM’s drop tower and Blue Origin’s New Shepard. The performance of representative electrolytic cells subject to different MHD regimes is addressed from an electrochemical and fluid dynamic perspectives. It is demonstrated that the MHD force effectively detaches and collects gas bubbles in microgravity while increasing the current density and improving the stability of the electrolytic cell. Ultimately, this opens the door for the development of highly-efficient space electrolytic cells with applications to human and robotic space exploration.
水电解是太空中生产氧气和氢气的基本化学过程。它广泛应用于现代环境控制和生命维持系统、推进技术和高密度储能装置中。此外,未来的行星际任务可能将水作为就地资源利用方法获取和处理的商品来生产推进剂,从而减少运载工具的发射质量。缺乏浮力是电解槽在低重力下运行的主要技术挑战。分离和收集氧气和氢气气泡的需要传统上是通过强制水再循环回路来解决的。然而,这导致了由多个元件和运动部件组成的复杂、低效和不可靠的液体管理装置。两种不同的磁流体动力学(MHD)机制可以用来诱导相分离:抗磁性和洛伦兹力。前者在强而不均匀的磁场存在下产生,并导致磁浮力效应。后者是在两个电极之间产生的电流上施加磁场的结果。这两种方法都有可能产生新一代的电解电池,其运动部件最少或没有,从而使人类的深空操作以最小的质量和功率损失为代价。需要专门的微重力实验来研究这些新的磁增强电解概念。本演讲介绍了这两种方法的基本原理,并讨论了在ZARM的drop tower和Blue Origin的New Shepard上进行的几次实验活动的实验设计和结果。从电化学和流体动力学的角度讨论了不同MHD制度下具有代表性的电解槽的性能。结果表明,在微重力条件下,MHD力可以有效地分离和收集气泡,同时增加了电流密度,提高了电解槽的稳定性。最终,这为开发高效的空间电解电池打开了大门,并将其应用于人类和机器人的太空探索。
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引用次数: 0
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