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

当与电池集成时，燃料电池可以用来显著增加电动汽车的续航里程，甚至有可能使远程电动飞机成为可能。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氢所需的大量能量输入限制了这种混合电力技术的日常运输应用。乙醇是一种在环境条件下的液体，构成了一种可再生的、高能量密度的氢的替代品，尽管缺点是乙醇必须在复杂的化学过程中重整成氢，然后才能供应给燃料电池。在这项提议中，乙醇重整过程将与燃料电池整合在一起，开发一种催化剂，在燃料电池的一个电极上完成这种化学转化，从而消除昂贵、沉重和能源密集型的重整过程。开发这种直进式乙醇燃料电池的学术研究人员将与日产合作，推进他们的e-Bio燃料电池汽车技术。如果成功，该项目的结果包括重整器/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。这项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。这项目标计划将通过学生实习计划支持工业和学术研究团队之间的紧密联系，向日产、华盛顿州立大学(WSU)和石溪大学(SBU)的研究生介绍涉及材料合成、催化剂工程和燃料电池技术的跨学科研究。拟议的工作将对以下方面产生广泛的影响：(1)通过西苏里州立大学多元文化学生服务办公室和密歇根州立大学的全纳教育计划，为未被充分代表的本科生提供研究经验；(2)通过与西苏里州立大学的帕劳斯发现科学中心和密歇根州立大学的STEM教育研究所合作，提高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性科学活动和参与ACS项目种子计划，吸引高中生进入科学和工程领域。这项研究计划的主要目标是(1)开发高度分散在三维有序介孔BaO基载体中的Mo掺杂Ni(Ni-Mo)纳米颗粒形式的乙醇重整催化剂，该催化剂能够在传统的镍基燃料阳极上作为内部乙醇重整层强烈地吸附和活化H2O，以及(2)考察直接进料乙醇金属支撑固体氧化物燃料电池(MS-SOFC)在预期运输条件下的催化剂性能。直接进料乙醇MS-SOFC的一个显著优势是不需要从外部将乙醇燃料转化为氢，因此操作简单；然而，在传统MS-SOFC操作的恶劣操作条件下，由于严重结焦，镍基阳极会迅速失活。为了解决这一问题，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重整层来设计多功能双层阳极。为了成功地制备这种双层阳极，PI首先通过控制Mo的掺杂水平来调节Ni-Mo纳米粒子的电子结构，然后将纳米粒子渗透到高比表面积的三维有序介孔BaZr0.4Ce0.4Y0.203(BZCY)载体中。用X-射线吸收光谱(XAS)和环境透射电子显微镜(E-TEM)测定了Ni-Mo/BZCY催化剂在标称的乙醇重整反应条件下的氧化状态和结构，以将这些测量结果与观察到的催化性能联系起来。PIS还将使用原位拉曼光谱和漂移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操作条件下的内重整和整体电化学活性。通过拟议的日产实习计划，研究生将与日产工程师合作，在与车辆操作相关的测试条件下，评估和验证日产具有内部重整层的MS-SOFC模型。通过这些路况测试，将评估直供乙醇MS-SOFC在一系列驾驶条件下的电能质量能力和性能。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

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 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 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.