Collaborative Research & GOALI: Direct-Fed Ethanol Metal-Supported Solid Oxide Fuel Cells

当与电池集成时，燃料电池可用于显着增加电动汽车的续航里程，甚至可能使长途电动飞机成为可能。然而，大多数燃料电池技术依赖于氢作为燃料，因此压缩氢气的低能量密度和生产低温液态氢所需的大能量输入限制了这种混合电能技术的日常运输应用。乙醇在环境条件下为液体，构成氢的可再生且高能量密度的替代物，尽管其缺点是乙醇必须在复杂的化学过程中重整为氢，然后才能进料至燃料电池。在该提议中，乙醇重整过程将通过开发在燃料电池电极之一上实现这种化学转化的催化剂与燃料电池集成，从而消除昂贵、繁重和能源密集的重整过程。开发这种直接进料乙醇燃料电池的学术研究人员将与日产北美公司合作。来推进他们的电子生物燃料电池汽车技术。如果成功，该项目的成果包括重整器/燃料电池系统的总重量/成本降低和简化的燃料电池内部设计。拟议的研究建立在日产和学术研究团队之间现有的合作基础上。该GOALI提案将通过学生实习计划支持工业和学术研究团队之间的密切联系，向研究生介绍日产，华盛顿州立大学（WSU）和斯托尼布鲁克大学（SBU）的跨学科研究，包括材料合成，催化剂工程和燃料电池技术。拟议的工作将对以下方面产生广泛影响：（1）通过WSU的多元文化学生服务办公室和SBU的全纳教育计划为代表性不足的本科生提供研究经验;（2）通过与WSU的帕卢塞发现科学中心和SBU的STEM教育研究所合作，促进公众对科学和工程重要性的认识;以及（3）通过指导高中团队参加地区科学活动和参与ACS项目SEED计划，吸引高中学生进入科学和工程领域。拟议研究的结果将通过正常的出版和技术会议上的介绍渠道广泛传播。为了追求能够实现长距离电力运输的实用直接进料乙醇燃料电池，该研究计划的主要目标是（1）开发以Mo掺杂的Ni（Ni-Mo）纳米颗粒形式高度分散在三层-尺寸有序的介孔BaO基载体，可以强烈地吸附和活化H2O作为传统Ni基燃料电池阳极上的内部乙醇重整层，和（2）研究在直接进料乙醇金属支撑的固体氧化物燃料电池（MS-SOFC）的运输应用预期的条件下的催化剂性能。直接进料乙醇MS-SOFC的显著优点是通过不必在外部将乙醇燃料改革为氢气而提供的简单性;然而，在常规MS-SOFC操作的苛刻操作条件下，Ni基阳极将由于严重的焦化而快速失活。为了解决这个问题，学术研究团队将通过电喷涂Ni-Mo纳米颗粒作为阳极表面的内部重整层来设计多功能双层阳极。为了成功地制造这种双层阳极，PI将首先通过控制Mo掺杂水平来调整Ni-Mo纳米颗粒的电子结构，然后将纳米颗粒渗透到高表面积、三维有序的介孔BaZr0.4Ce0.4Y0.2O3（BZCY）载体中。将使用操作X射线吸收光谱（XAS）和环境透射电子显微镜（E-TEM）来确定在标称乙醇重整反应条件下Ni-Mo/BZCY催化剂的氧化态和结构，以将这些测量与观察到的催化性能相关联。PI还将使用原位拉曼和DRIFT光谱来研究催化剂分子结构与重整反应机理之间的关系。基于确定的结构-活性关系，PI将在MS-SOFC阳极上制备高性能的Ni-Mo/BZCY内部重整层，并将使用原位拉曼光谱电化学系统来研究其在实际SOFC操作条件下的内部重整和总体电化学活性。通过拟议的日产北美公司。实习计划，研究生将与日产工程师一起评估和验证模型MS-SOFC与内部重整层在日产在测试条件下相关的车辆操作。从这些道路剖面测试，电力质量能力和性能的直接饲料乙醇MS-SOFC下的一系列驾驶条件将进行评估。这个奖项反映了NSF的法定使命，并已被认为是值得支持的，通过评估使用基金会的智力价值和更广泛的影响审查标准。

When integrated with batteries, fuel cells can be used to significantly increase the range of electric vehicles, potentially even making long-haul electric aircraft possible. Most fuel cell technologies, however, rely on hydrogen as the fuel and so the low energy density of compressed hydrogen gas and the large energy input needed to produce cryogenic liquid hydrogen limit every-day transportation applications of this hybrid electrical energy technology. Ethanol, a liquid under ambient conditions, constitutes a renewable and high energy density alternative to hydrogen, albeit with the drawback that the ethanol must be reformed to hydrogen in a complex chemical process before it can be fed to the fuel cell. In this proposal, the ethanol reforming process will be integrated with the fuel cell by developing a catalyst that accomplishes this chemical transformation on one of the fuel cell electrodes, eliminating the costly, heavy, and energy intensive reforming process. The academic researchers developing this direct-feed ethanol fuel cell will partner with Nissan North America, Inc. to advance their e-Bio Fuel-Cell automotive technology. If successful, the outcomes of this project include a total weight/cost reduction of the reformer/fuel cell system and a simplified fuel cell internal design. The proposed research builds on an existing collaboration between Nissan and the academic research team. This GOALI proposal will support this close link between the industrial and academic research teams through a student internship program, introducing graduate students to interdisciplinary research involving material synthesis, catalyst engineering, and fuel cell technology at Nissan, Washington State University (WSU), and Stony Brook University (SBU). The proposed work will have broad impact on (1) research experiences for underrepresented undergraduate students through the Office of Multicultural Student Services at WSU and the Inclusive Education program at SBU; (2) promoting public awareness of the importance of science and engineering by collaborating with the Palouse Discovery Science Center at WSU and the Institute for STEM Education at SBU; and (3) attracting high school students to the fields of science and engineering by mentoring a high school team for regional science events and participating in the ACS Project SEED Program. The results of the proposed research will be disseminated widely through the normal channels of publication and presentation at technical meetings.In pursuit of practical direct-feed ethanol fuel cells that will enable long-distance electric transportation, the primary aims of this research program are to (1) develop ethanol reforming catalysts in the form of Mo-doped Ni (Ni-Mo) nanoparticles highly dispersed within a three-dimensionally ordered mesoporous BaO-based support that can strongly adsorb and activate H2O as the internal ethanol reforming layer over the conventional Ni-based fuel call anode, and (2) investigate the catalyst performance under conditions expected for transportation applications of direct-feed ethanol metal-supported solid oxide fuel cells (MS-SOFCs). A significant advantage of a direct-feed ethanol MS-SOFC is the simplicity afforded by not having to externally reform the ethanol fuel to hydrogen; however, under the harsh operating conditions of conventional MS-SOFC operation, the Ni-based anodes would quickly deactivate due to severe coking. To address this issue, the academic research team will design the multifunctional bilayer anode by electro-spraying Ni-Mo nanoparticles as the internal reforming layer over the anode surface. To successfully fabricate this bilayer anode, the PIs will first tune the electronic structure of Ni-Mo nanoparticle by controlling the Mo doping level and then infiltrate the nanoparticles into the high surface area, three-dimensionally ordered mesoporous BaZr0.4Ce0.4Y0.2O3 (BZCY) support. Operando X-ray absorption spectroscopy (XAS) and environmental transmission electron microscopy (E-TEM) will be used to determine the oxidation state and structure of the Ni-Mo/BZCY catalysts under the nominal ethanol-reforming reaction conditions to relate those measurements to observed catalytic performance. The PIs will also use in-situ Raman and DRIFT spectroscopy to investigate the relationship between catalyst molecular structure and reforming reaction mechanisms. Based on the identified structure-activity relationships, the PIs will fabricate the high-performance Ni-Mo/BZCY internal reforming layer over the MS-SOFC anode and will use an in-situ Raman spectroelectrochemical system to investigate its internal reforming and overall electrochemical activity under actual SOFC operating conditions. Through the proposed Nissan North America, Inc. internship program, graduate students will work with Nissan engineers to evaluate and validate model MS-SOFCs with the internal reforming layer at Nissan under test conditions relevant to the vehicle operation. From these road profile tests, the power quality capability and performance of the direct-feed ethanol MS-SOFCs under a range of driving conditions will be assessed.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.