Single-particle electrochemistry to identify fundamental barriers to magnesium ion intercalation in transition metal oxides

单粒子电化学确定过渡金属氧化物中镁离子嵌入的基本障碍

• 批准号: 2312359
• 负责人: Robert Klie
• 金额: $ 69.91万
• 依托单位: University of Illinois at Chicago
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-08-15 至 2026-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2312359&HistoricalAwards=false
• 关键词: Single; particle; electrochemistry; identify; fundamental

Li-ion batteries have seen a steady growth in achievable energy storage capacity and durability over the last several years, rendering them the dominant market player. However, accelerating the transition to a society based on renewable energy still requires new alternative battery chemistries. One possible solution is to replace lithium ions as the primary carriers of electronic charges by multivalent carriers like magnesium. The theoretical gains with the use of magnesium are hampered by the inefficient transport of magnesium within the battery at relevant temperatures of operation, especially in the solid oxide cathodes needed for transformational gains in energy density. In this project, novel approaches of electron microscopy are combined to examine the intrinsic reactivity of model transition metal oxides as cathodes in Mg-ion batteries. These approaches will isolate the behavior of individual electrode particles from the effect of the complex architectures used in conventional electrodes and reveal the balance between productive and competing processes at the atomic scale. This project will quantify critical bottlenecks in the development of high-energy batteries based on magnesium to unlock the next generation of rechargeable devices. The project’s activities center around education and training providing the diverse student body at University of Illinois - Chicago (UIC), a Research-1 Hispanic-serving institution with opportunities for hands-on research and learning experiences in cutting-edge electrochemistry, materials science, and characterization research. The integration of research and education through the training of undergraduate and graduate students in state-of-the-art in-situ scanning transmission electron microscopy and electrochemistry is an integral feature of this project.This research project seeks to identify and overcome the fundamental barriers of efficient Mg-ion intercalation in transition metal oxide cathodes using a combination of cathode synthesis, electrochemistry, and state-of-the-art electron microscopy. Several oxides have now been shown to be active toward Mg intercalation, yet the process demands high temperature and is accompanied by an unacceptably high hysteresis, a fatal flaw for practical application. This project focuses on MgV2O4 as a model system to unravel the fundamental barriers to efficient Mg2+ intercalation by conducting measurements on single particle cathodes, revealing the intrinsic behavior of the material, rather than the convolution of cell design and transport across a complex electrode architecture. Novel in-situ holders, thin-film model system cathodes and scanning transmission electron microscopy provide an atomic-scale description of bulk and interfacial transformations of single particles during electrochemical cycling, separating changes due to reversible intercalation from irreversible competing reactions. The evaluation of reactivity at multiple temperatures will provide unique insight into the kinetic limitations of the structural transitions, charting a path for Mg-based cathodes towards a battery at, or near, room temperature.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.

在过去的几年里，锂离子电池在可实现的储能容量和耐用性方面稳步增长，使其成为主导市场参与者。然而，加速向基于可再生能源的社会转型仍然需要新的替代电池化学物质。一种可能的解决方案是用镁等多价载体取代锂离子作为电子电荷的主要载体。使用镁的理论收益受到镁在相关操作温度下在电池内的低效运输的阻碍，特别是在能量密度的转换增益所需的固体氧化物阴极中。在这个项目中，电子显微镜的新方法相结合，以检查模型过渡金属氧化物作为镁离子电池阴极的固有反应性。这些方法将把单个电极颗粒的行为与传统电极中使用的复杂结构的影响隔离开来，并揭示原子尺度上生产过程和竞争过程之间的平衡。该项目将量化基于镁的高能电池开发的关键瓶颈，以解锁下一代可充电设备。该项目的活动中心围绕教育和培训提供伊利诺伊大学-芝加哥（UIC），一个研究-1西班牙裔服务机构的多样化的学生团体，在尖端的电化学，材料科学和表征研究的动手研究和学习经验的机会。本项目的一个主要特点是通过培养本科生和研究生，使他们掌握最先进的原位扫描透射电子显微镜和电化学，从而实现研究与教育的一体化。本研究项目旨在确定并克服过渡金属氧化物阴极中有效镁离子嵌入的基本障碍，采用阴极合成、电化学和电化学相结合的方法。和最先进的电子显微镜几种氧化物现已被证明对镁的嵌入是积极的，但该过程需要高温，并伴随着不可接受的高滞后，实际应用的致命缺陷。该项目的重点是MgV 2 O 4作为一个模型系统，通过对单粒子阴极进行测量，揭示材料的内在行为，而不是电池设计和复杂电极结构的运输的卷积，来解开有效Mg 2+嵌入的基本障碍。新的原位持有人，薄膜模型系统阴极和扫描透射电子显微镜提供了一个原子尺度的描述，在电化学循环过程中的单个颗粒的体和界面的转变，分离的变化，由于可逆的嵌入不可逆的竞争反应。在多个温度下的反应性评估将为结构转变的动力学限制提供独特的见解，为镁基阴极在室温或接近室温的电池绘制路径。该奖项反映了NSF的法定使命，并被认为值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估来支持。