CAREER: Investigation of Non-Aqueous Single-Metal Redox Flow Batteries through Experiment and Modeling

职业：通过实验和建模研究非水单金属氧化还原液流电池

• 批准号: 1253544
• 负责人: Charles Monroe
• 金额: $ 40万
• 依托单位: Regents of the University of Michigan - Ann Arbor
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-02-01 至 2015-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1253544&HistoricalAwards=false
• 关键词: CAREER; Investigation; Non; Aqueous; Single

Intellectual Merit: This proposal focuses on experimental and theoretical studies of a new class of non-aqueous, single-metal redox flow battery (RFB). These RFBs rely on disproportionation of metal coordination complexes into oxidized and reduced products. Use of non-aqueous liquids to support redox reactions makes it possible to raise cell voltages well above the range where water decomposes. Our preliminary experiments using first-row transition-metal complexes demonstrate some equilibrium voltages more than twice as large as aqueous systems permit, suggesting that development of high-conductivity solvent/support systems and highly soluble active-complex structures that undergo multiple electron transfer could improve energy density by 200%-300%. Non-aqueous, single-metal, disproportionation-based RFBs promise significantly improved performance over aqueous chemistries, and our preliminary cycling results suggest competitive coulombic efficiencies. We see comparatively low energy and power efficiencies in non-aqueous RFB systems during cycling, issues this research will address. The proposed research will perform and rationalize experimental observations of non-aqueous RFBs. Our goal is to guide reactor design and materials selection for next-generation nonaqueous RFBs on the basis of sound fundamental principles. Three complementary projects will be executed in parallel during the five-year research term. (1) Equilibrium electrochemical properties of various non-aqueous RFB systems will be investigated by potentiometric and spectroscopic methods. Several trivalent β-diketonate metal active complexes will be studied in various support and solvent systems. In addition to elucidating how activity and potential depend on an RFB system?s state of charge, this work will inform future system design by showing how solute/solute and solute/solvent interactions impact efficiency of RFBs in general.(2) Transport phenomena in the liquid and separator phases will be characterized with methods including DC conductimetry, AC impedance spectroscopy, and UV-vis spectroscopy. The results will be matched to advanced theoretical multicomponent transport models, and used to underpin a property database for computer simulations of RFB operation. RFB cells will be fabricated to corroborate numerical results with experimental charge/discharge data. The model will also be used to predict how control schemes and cell design can be varied to optimize RFB performance. (3) Reaction rates and mechanisms in single-metal RFBs will be probed by electrochemical experiments. Theoretical methods will be created to establish mechanisms for several active-complex redox reactions. Kinetic models will be included in RFB cell simulations. Ultimately, this research program will deliver a continuum-scale model that rationalizes and predicts the transient current/voltage response of RFB cells during practical charging and discharging between various states of charge, and at various charge and discharge rates. Simulations will permit studies of various electrode configurations, cell designs, and electrolyte flow schemes. We will take a bottom-up approach, using studies of bulk, interfacial, and phase exchange processes to support a holistic, microscopically informed model of the entire RFB.Broader Impact: Outreach activities will foster the natural connection that I believe to exist between research progress and pedagogical activity. My central outreach objective is to advocate multidisciplinary, collaborative electrochemical engineering education in a diverse research environment. This objective will be addressed by: (1) continuing development of graduate-level electrochemical engineering courses that incorporate RFB research problems; (2) encouraging undergraduate interest in energy-system design by participating in service activities related to electrochemical engineering, offering undergraduate research opportunities, and developing forums outside the classroom for the exchange of ideas; and (3) taking part in the MI-LSAMP outreach program, which aims to increase participation by under-represented minorities and women in cutting-edge science, technology, engineering, and mathematics. I hope to move electrochemistry away from the periphery of chemical engineering research.Increasing the exposure of pre-college, undergraduate, and graduate students from all walks of life to electrochemical engineering will facilitate the innovation necessary to support a national shift to more diverse, sustainable energy production.

智力优势：本论文的主要工作是对新型非水单金属液流电池（RFB）进行实验和理论研究。这些RFB依赖于将金属配位络合物转化为氧化和还原产物。使用非水液体来支持氧化还原反应使得可以将电池电压提高到远高于水分解的范围。我们使用第一行过渡金属配合物的初步实验表明，一些平衡电压是水溶液系统允许的两倍以上，这表明开发高电导率溶剂/支持系统和高度可溶的活性配合物结构，进行多电子转移可以提高能量密度200%-300%。非水，单金属，基于反硝化的RFBs承诺显着改善性能超过水化学，我们的初步循环结果表明竞争力的库仑效率。我们看到非水RFB系统在循环过程中的能量和功率效率相对较低，本研究将解决这些问题。拟议的研究将执行和合理化非水RFBs的实验观察。我们的目标是指导反应器的设计和材料的选择，为下一代非水RFBs的基础上健全的基本原则。三个互补的项目将在五年的研究期间并行执行。(1)各种非水RFB系统的平衡电化学性质将通过电位和光谱方法进行研究。几个三价的#946;-二酮金属活性配合物将在各种支持和溶剂系统进行研究。除了阐明活动和潜力如何取决于RFB系统？的充电状态，这项工作将告知未来的系统设计，显示溶质/溶质和溶质/溶剂的相互作用如何影响效率的RFBs一般。(2)液相和分离相的传输现象将采用包括直流电导法、交流阻抗谱和紫外-可见光谱的方法进行表征。结果将匹配先进的理论多组分传输模型，并用于支持计算机模拟RFB操作的属性数据库。将制造RFB电池以证实数值结果与实验充电/放电数据。该模型还将用于预测控制方案和电池设计如何变化以优化RFB性能。(3)在单金属RFBs的反应速率和机制将通过电化学实验来探讨。将创建理论方法来建立几个活性复杂的氧化还原反应的机制。动力学模型将纳入RFB细胞模拟。最终，该研究计划将提供一个连续规模的模型，合理化和预测RFB电池在各种充电状态之间的实际充电和放电过程中的瞬态电流/电压响应，以及各种充电和放电速率。模拟将允许各种电极配置，电池设计和电解质流动方案的研究。我们将采取自下而上的方法，使用大量的研究，界面，和相交换过程，以支持一个整体的，微观上知情的整个RFB.Broader影响模型：外展活动将促进自然的联系，我相信研究进展和教学活动之间存在。我的中心外展目标是倡导多学科，合作电化学工程教育在一个多样化的研究环境。这一目标将通过以下方式实现：（1）继续发展研究生水平的电化学工程课程，其中包括RFB研究问题;（2）通过参加与电化学工程有关的服务活动，提供本科生研究机会，并在课堂外建立交流思想的论坛，鼓励本科生对能源系统设计的兴趣;以及（3）参加MI-LSAMP外展计划，该计划旨在增加代表性不足的少数民族和妇女在尖端科学，技术，工程和数学方面的参与。我希望将电化学从化学工程研究的边缘移开。增加来自各行各业的大学预科生，本科生和研究生对电化学工程的接触将促进必要的创新，以支持国家向更多样化，可持续的能源生产的转变。