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Effects of Oxygen Defects in Zr Oxide-Based Thin Films on Oxygen Reduction Reaction in Acidic Media 氧化锆基薄膜中氧缺陷对酸性介质中氧还原反应的影响
Pub Date : 2023-09-29 DOI: 10.1149/11204.0343ecst
Yuri Watanabe, Koichi Matsuzawa, Ryuji Monden, Takaaki Nagai, Akimitsu Ishihara
Zirconium oxide thin films were prepared by RF magnetron sputtering as model catalysts for oxygen reduction reaction (ORR) in acidic media. The effects of sputtering conditions on ORR activity in acidic media was investigated. The effect of the deposition temperature on the ORR activity depended on whether the deposition atmosphere contained oxygen (Ar+O 2 , Ar+N 2 +O 2 ) or only nitrogen (Ar+N 2 ). In the range of 300-800 °C of the deposition temperature, the electrodes prepared in an Ar+N 2 showed higher ORR activity. XRD and XPS results showed that the tetragonal phase grew in an Ar+N 2 atmosphere, while a mixed phase of tetragonal and monoclinic phases grew in an Ar+O 2 atmosphere. It was found that Zr oxide thin film with a high proportion of tetragonal phase showed high ORR activity.
采用射频磁控溅射法制备氧化锆薄膜作为酸性介质中氧还原反应(ORR)的模型催化剂。研究了在酸性介质中溅射条件对ORR活性的影响。沉积温度对ORR活性的影响取决于沉积大气中是否含有氧(Ar+ o2, Ar+ n2 + o2)或仅含氮(Ar+ n2)。在300 ~ 800℃的沉积温度范围内,用Ar+ n2制备的电极表现出较高的ORR活性。XRD和XPS结果表明,在Ar+ n2气氛中生长四方相,而在Ar+ o2气氛中生长四方相和单斜相的混合相。结果表明,四方相比例高的氧化锆薄膜具有较高的ORR活性。
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引用次数: 0
(Invited) On Degradation Mechanisms of Ni-YSZ Fuel Electrodes in Solid Oxide Cells (特邀)Ni-YSZ燃料电极在固体氧化物电池中的降解机理
Pub Date : 2023-09-29 DOI: 10.1149/11205.0071ecst
Mogens Bjerg Mogensen, Gurli Mogensen
This is a continuation of a series of articles by the principal author on degradation of Ni-YSZ cermet electrodes. This one gives a brief listing of the main aspects and in particular of the disagreements in literature on the long term degradation mechanisms of Ni-YSZ electrodes at high current density. Two main hypotheses are presented, and the weaknesses and strengths are briefly discussed. Recommendations for alleviation of the degradation are given as well as for needed experiments in the future.
这是主要作者关于Ni-YSZ金属陶瓷电极降解的一系列文章的延续。本文简要列出了主要方面,特别是文献中关于Ni-YSZ电极在高电流密度下的长期降解机制的分歧。提出了两种主要假设,并简要讨论了其优缺点。提出了减轻退化的建议以及今后需要进行的实验。
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引用次数: 0
Corrosion Behaviour of Ni-Based Alloys 230, 617 and 601 in CO2 Gas at 750 and 850°C 镍基合金230、617和601在750和850℃CO2气体中的腐蚀行为
Pub Date : 2023-09-29 DOI: 10.1149/11205.0003ecst
Haoyi Li, Thuan Nguyen, Jianqiang Zhang, David Young
This paper investigated corrosion behaviors of three nickel-based chromia-forming commercial alloys (230, 617 and 601) at 750°C and 850°C in a CO 2 environment for up to 500 h. All three alloys showed good oxidation resistance by forming mainly a protective chromia layer with low weight changes. Internal Al 2 O 3 was precipitated beneath a thin protective chromia layer for all cases. For 230 and 617 alloys, NiO and Cr-rich spinel outer layers were formed, but for 601 less iron and nickel outward diffusion was observed at both temperatures. Furthermore, some minor alloy elements (Mn, Ti, and Co) were observed to diffuse into the chromia layers.Wagner’s theory predicted that alloy concentrations were marginal for chromia formation at both temperatures for the test alloys. The observation of protective chromia formation can be attributed to the effect of other alloying elements, e.g. Al, Mn, Ti, Si etc. Wagner’s theory also predicted that this critical chromium concentration decreased with increasing the oxidation temperature, which is consistent with the experimental observation.The Al and Si oxides formed an additional protective barrier between the matrix and the chromia layer, preventing the diffusion of iron and nickel outwards and therefore increasing oxidation resistance. Manganese effectively prevented carburization by combining with chromia to form the outermost spinel oxide layer, increasing oxidation/carburisation resistance. Titanium diffused through the chromia layer, accelerating chromium diffusion and leading to higher kinetic rates. Tungsten reduced oxidation resistance by increasing the metal vacancies and therefore outward diffusion of Ni, Fe and Mn through the chromia scale.
研究了三种镍基成铬合金(230、617和601)在750°C和850°C的CO 2环境中长达500 h的腐蚀行为。这三种合金都表现出良好的抗氧化性,主要形成一个保护铬层,重量变化小。在所有情况下,内部的al2o3都沉淀在一层薄薄的保护铬层下。对于230和617合金,形成了富NiO和cr的尖晶石外层,但对于601合金,在两个温度下都观察到少量铁和镍的向外扩散。此外,还观察到少量合金元素(Mn、Ti和Co)扩散到铬层中。瓦格纳的理论预测,合金浓度在两种温度下对测试合金的铬形成都是边际的。观察到保护性铬的形成可归因于其他合金元素,如Al, Mn, Ti, Si等的作用。Wagner的理论也预测了这个临界铬浓度随着氧化温度的升高而降低,这与实验观察一致。铝和硅氧化物在基体和铬层之间形成了额外的保护屏障,防止铁和镍向外扩散,从而增加了抗氧化性。锰与铬结合形成最外层尖晶石氧化层,有效地阻止了渗碳,提高了抗氧化/渗碳能力。钛通过铬层扩散,加速了铬的扩散,导致了更高的动力学速率。钨通过增加金属空位来降低抗氧化性,从而使Ni、Fe和Mn通过铬层向外扩散。
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引用次数: 0
Visualization of Oxygen Bubbles on a Flat Ionomer-Coated Platinum Electrode 平面离聚物铂电极上氧气泡的可视化
Pub Date : 2023-09-29 DOI: 10.1149/11204.0463ecst
Hideki Suwa, Ryo Kanemoto, Kohei Toyama, Sota Kishi, Takuto Araki
To improve the performance of polymer electrolyte membrane water electrolyzers (PEMWE), it is necessary to grasp oxygen transport from the reaction site. This paper presents a visualization study which examines the effect of ionomers on the behavior of oxygen bubbles generated from catalyst covered with ionomers. The bubbles are captured with a high-speed camera, and the post visualization by electron microscopy with EDX showed that there were no significant cracks and damages on the ionomers. This implies that oxygen bubbles are generated on the ionomer surface without an apparent three-phase boundary (i.e., catalyst-ionomer-water). This suggests oxygen generated on the Pt surface was transported as dissolved oxygen through the ionomer layer.
为了提高聚合物电解质膜水电解槽(PEMWE)的性能,有必要掌握反应现场的氧气输送。本文提出了一种可视化研究方法,考察了离子对覆盖在催化剂上的氧气泡行为的影响。用高速摄像机捕获气泡,并用EDX电镜观察后发现,离子单体上没有明显的裂纹和损伤。这意味着氧气泡产生在离子表面没有明显的三相边界(即,催化剂-离子-水)。这表明Pt表面产生的氧以溶解氧的形式通过离子层进行输送。
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引用次数: 0
Liquid Water Permeability in a Hydrophobic Microporous Layer for the Anode Interdigitated Flow Field of a Gas-Liquid Separating Polymer Electrolyte Membrane Water Electrolyzer 疏水微孔层中液态水在气液分离聚合物电解质膜式电解槽阳极交叉流场中的渗透性
Pub Date : 2023-09-29 DOI: 10.1149/11204.0207ecst
Shunji Kubota, Hironori Nakajima, Motohiko Sato, Asuka Shima, Masato Sakurai, Yoshitsugu Sone
A novel interdigitated flow field for polymer electrolyte membrane water electrolyzers composed of oxygen exhaust channels apart from liquid water feed channels has been developed for ground and space applications. This design can internally separate oxygen gas and liquid water between the flow channels, dispensing with water circulators for bubble removal and external separators with natural or centrifugal buoyancy. In this electrolyzer, pressurized liquid water is injected in the in-plane direction from the water channels to the catalyst layer through the hydrophobic microporous layer (MPL) of the anode porous transport layer. The produced oxygen gas is discharged in the through-plane direction of the MPL, taking advantage of the capillary pressure in the MPL. This study conducted liquid water permeability tests on the MPL with pressurized water. We find gradual permeability decreases with time for different liquid water pressures. The permeability will be a useful parameter for the optimal structural designs of this electrolyzer.
在地面和空间应用中,开发了一种由除液态水进料通道外的氧气排气通道组成的新型聚合物电解质膜式水电解槽的交错流场。这种设计可以在内部分离气流通道之间的氧气和液态水,省去了用于去除气泡的水循环器和具有自然浮力或离心浮力的外部分离器。在该电解槽中,加压液态水通过阳极多孔传输层的疏水微孔层(MPL)从水道沿平面方向注入催化剂层。利用MPL内的毛细压力,产生的氧气沿MPL的通平面方向排出。采用加压水对MPL进行了液态水渗透性试验。我们发现,对于不同的液态水压力,渗透率随时间逐渐降低。磁导率是电解槽结构优化设计的重要参数。
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引用次数: 0
Development of MEAs Using Mesoporous Carbon Fibers as Cathode Carbon Supports 介孔碳纤维作为阴极碳载体的MEAs研究进展
Pub Date : 2023-09-29 DOI: 10.1149/11204.0405ecst
Daichi Yasufuku, Kazunari Sasaki, Akari Hayashi
Mesoporous carbon fibers were synthesized and ball-milled into fine carbon particles to use as cathode carbon support. A critical issue of high ohmic overvoltage, previously found in mesoporous carbon related supports, was successfully reduced. Reducing carbon particle size was realized to be important in order to lower interparticle resistance and further to lower ohmic resistance. When cathodes were successfully prepared, low concentration overvoltage was found to a beneficial point of using mesoporous carbon based supports. Resulting low concentration overvoltage could not be explained by the difference in macro-porous structure of the cathode. Therefore, mesopores are expected to play an important role of the mass transfer, even though the exact mechanism is still under the study.
合成了介孔碳纤维,并将其球磨成细小的碳颗粒作为阴极碳载体。先前在介孔碳相关支架中发现的高欧姆过电压的关键问题已成功降低。减小碳颗粒尺寸是降低颗粒间电阻和进一步降低欧姆电阻的重要途径。当阴极制备成功时,发现低浓度过电压是使用介孔碳基支架的有利点。造成的低浓度过电压不能用阴极大孔结构的差异来解释。因此,介孔有望在传质中发挥重要作用,尽管确切的机制仍在研究中。
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引用次数: 0
(Invited) Characteristics of GaN/High-k Capacitors Under Positive Bias Stress (特邀)GaN/高k电容器在正偏置应力下的特性
Pub Date : 2023-09-29 DOI: 10.1149/11201.0109ecst
Toshihide Nabatame, Tomomi Sawada, Yoshihiro Irokawa, Yasuo Koide, Kazuhito Tsukagoshi
We investigated characteristics of the Hf 0.55 Al 0.45 O x MOS capacitor (HfAlO) under a high sweep voltage and positive bias stress (PBS). The role of a 0.5nm-thick HfO 2 (HfO/HfAlO) or a 0.5nm-thick Al 2 O 3 (AlO/HfAlO) interfacial layer (IL) between n-GaN and Hf 0.55 Al 0.45 O x film on electrical properties was also discussed. The HfAlO, HfO/HfAlO and AlO/HfAlO capacitors showed a similar leakage current property. Each flatband voltage (V fb ) exhibited the same value against electric field (E) from V fb . No V fb hysteresis of all capacitors was observed at high Es from V fb up to 3.5MVcm -1 . Under PBS, the positive V fb shift appeared in all capacitors and increased with increasing the E from V fb . Note that the positive V fb shift suppressed 0.3V regardless of IL even in high effective electric field from V fb regions of 10~15MVcm -1 while the positive V fb shift of the Al 2 O 3 capacitor significantly increased above 0.5V at a low 6.5MVcm -1 .
研究了高频0.55 Al 0.45 O x MOS电容器(HfAlO)在高扫描电压和正偏置应力(PBS)作用下的特性。讨论了n-GaN与Hf 0.55 Al 0.45 O x膜之间0.5nm厚的HfO 2 (HfO/HfAlO)或0.5nm厚的al2o3 (AlO/HfAlO)界面层(IL)对电性能的影响。HfAlO、HfO/HfAlO和AlO/HfAlO电容器具有相似的漏电流特性。每个平带电压(vfb)对电场(E)的值相同。在从V fb到3.5MVcm -1的高Es下,所有电容器均未观察到V fb迟滞现象。在PBS作用下,所有电容器都出现了正的vfb位移,并且随着来自vfb的E的增加而增加。注意,即使在10~15MVcm -1的vfb区域的高有效电场中,与IL无关,正vfb位移也抑制了0.3V,而al2o3电容器的正vfb位移在低6.5MVcm -1时显著增加到0.5V以上。
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引用次数: 0
Modeling of Proton Exchange Membrane Fuel Cell Stack and Start Strategy Optimization with a Multi-Objective Genetic Algorithm 质子交换膜燃料电池堆建模及多目标遗传算法启动策略优化
Pub Date : 2023-09-29 DOI: 10.1149/11204.0243ecst
Zhao Liu, Hui Cui Chen, Tong Zhang, Thomas von Unwerth, Carmen Meuser
This paper proposes a non-dominated sorting genetic algorithm II (NSGA-II) for optimizing the startup strategy of a proton exchange membrane fuel cell (PEMFC) stack to improve the dynamic response capability, output voltage, and net power. First, a Simulink model of the PEMFC stack including the anode module, cathode module, water transfer module, output voltage module, and output net power module is established, and the accuracy of the stack model is verified through experiments. The three performances are then optimized simultaneously based on NSGA-II. The results show that the optimized start-up loading strategy results in a PEMFC stack that outperforms the base model in steady-state voltage, undershoot percent, and net power these three indicators with the same response time, demonstrating the success of the method in solving multiple optimization problems. This study presents an effective approach for the multi-objective optimization of the PEMFC stack, which is of guidance for engineering practice.
本文提出了一种非支配排序遗传算法II (NSGA-II),用于优化质子交换膜燃料电池(PEMFC)堆栈的启动策略,以提高其动态响应能力、输出电压和净功率。首先,建立了包括阳极模块、阴极模块、输水模块、输出电压模块和输出净功率模块在内的PEMFC堆叠的Simulink模型,并通过实验验证了堆叠模型的准确性。然后基于NSGA-II对三种性能进行同步优化。结果表明,优化后的启动负载策略使PEMFC堆栈在稳态电压、欠燃率和净功率这三个指标上优于基本模型,且响应时间相同,表明该方法在解决多个优化问题方面取得了成功。该研究为PEMFC堆的多目标优化提供了一种有效的方法,对工程实践具有指导意义。
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引用次数: 0
Infrared Spectroscopy Study of Edge Water Penetration at Hydrophilic Bonding Interface 亲水性键合界面边水渗透的红外光谱研究
Pub Date : 2023-09-29 DOI: 10.1149/11203.0031ecst
Paul Noël, Vincent Larrey, Christophe Morales, Francois Rieutord, Didier Landru, Frank Fournel
In this article, we report on the use of a new characterization technique to measure the water penetration at the bonding interfaces and to quantify it. This complements previous studies done using X-ray reflectometry and surface acoustic microscopy: Fourier Transform Infra-Red Multiple Internal Reflection (FTIR-MIR) spectroscopy is used here to characterize the evolutions of contributions of silanols, surface bonded water and free liquid water groups.
在本文中,我们报告了使用一种新的表征技术来测量键合界面上的水渗透并对其进行量化。这补充了先前使用x射线反射法和表面声学显微镜进行的研究:傅里叶变换红外多次内反射(FTIR-MIR)光谱在这里用于表征硅烷醇,表面键合水和自由液态水基团的贡献演变。
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引用次数: 0
A Study on Electrochemical Properties of Fuel-Electrode-Supported Reversible Solid Oxide Cells 燃料电极支撑可逆固体氧化物电池的电化学性能研究
Pub Date : 2023-09-29 DOI: 10.1149/11205.0141ecst
Ryota Ozaki, Kei Yamada, Kazutaka Ikegawa, Tsutomu Kawabata, Chie Uryu, Yuya Tachikawa, Junko Matsuda, Kazunari Sasaki
Reversible solid oxide cells (r-SOCs) enable both fuel cell power generation and steam-electrolysis hydrogen production by changing the direction of the current in the cells. They are attractive electrochemical devices because of their ability to regulate power supply derived from renewable energy sources. In this study, initial performance was evaluated, and an electrolyte-supported cell and fuel-electrode-supported cells were compared and evaluated with changing operating temperatures. The performances for fuel-electrode-supported cells with various combinations of fuel electrode and electrolyte materials were also evaluated. In addition, the Ni-YSZ/YSZ fuel-electrode-supported cell, which exhibited the highest current-voltage characteristics, was subjected to r-SOC cycling tests to evaluate the cycle durability.
可逆固体氧化物电池(r- soc)通过改变电池内电流的方向,使燃料电池发电和蒸汽电解制氢成为可能。它们是有吸引力的电化学装置,因为它们能够调节来自可再生能源的电力供应。在这项研究中,对初始性能进行了评估,并在不同的工作温度下对电解质支撑电池和燃料电极支撑电池进行了比较和评估。并对不同燃料电极和电解质材料组合的燃料电极支撑电池进行了性能评价。此外,Ni-YSZ/YSZ燃料电极支撑电池表现出最高的电流电压特性,并进行了r-SOC循环测试,以评估循环耐久性。
{"title":"A Study on Electrochemical Properties of Fuel-Electrode-Supported Reversible Solid Oxide Cells","authors":"Ryota Ozaki, Kei Yamada, Kazutaka Ikegawa, Tsutomu Kawabata, Chie Uryu, Yuya Tachikawa, Junko Matsuda, Kazunari Sasaki","doi":"10.1149/11205.0141ecst","DOIUrl":"https://doi.org/10.1149/11205.0141ecst","url":null,"abstract":"Reversible solid oxide cells (r-SOCs) enable both fuel cell power generation and steam-electrolysis hydrogen production by changing the direction of the current in the cells. They are attractive electrochemical devices because of their ability to regulate power supply derived from renewable energy sources. In this study, initial performance was evaluated, and an electrolyte-supported cell and fuel-electrode-supported cells were compared and evaluated with changing operating temperatures. The performances for fuel-electrode-supported cells with various combinations of fuel electrode and electrolyte materials were also evaluated. In addition, the Ni-YSZ/YSZ fuel-electrode-supported cell, which exhibited the highest current-voltage characteristics, was subjected to r-SOC cycling tests to evaluate the cycle durability.","PeriodicalId":11473,"journal":{"name":"ECS Transactions","volume":"39 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135198915","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
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ECS Transactions
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