NSF/DMR-BSF: The Effects of Configurational Disorder on Polaron Transport

NSF/DMR-BSF：构型无序对极化子传输的影响

• 批准号: 1809429
• 负责人: Richard Robinson
• 金额: $ 58.04万
• 依托单位: Cornell University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-08-15 至 2023-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1809429&HistoricalAwards=false
• 关键词: NSF; DMR; BSF; Effects; Configurational

Nontechnical Abstract: Oxides are well known as materials with low electronic conductivity. But upon closer examination, there is a great deal of variability in their ability to conduct charge, and much of this is unexplained. For instance, in cobalt manganese oxides the conductivity can increase up to 10 times depending on the cobalt to manganese ratio. The existing theories are accurate when there are only two components, for instance, just cobalt and oxygen, but when a third component is included, the theories break down. In this project, the team is investigating a fundamental question of oxides: how does atomic disorder affect conductivity in oxides. By elucidating these mechanisms, the team is opening up new avenues to tailor the conductivity in oxides, important for applications that rely on the insulating properties of oxides, as in semiconductor transistors, or for applications that could benefit from increased conductivity, as in batteries and fuel cells. To disseminate and promote science to the public the team is creating a website with on-line training videos to strengthen international science outreach and the US-Israel partnership using science for peaceful purposes, and the team is designing a module on electronic conductivity in oxides for Lending Library Experiments. The kit aligns with specific Next Generation Science Standards and uses exploratory hands-on activities to help experiential learning.Technical Abstract: The purpose of this work is to investigate a fundamental question in ternary oxides: how do charge carriers move through a spinel crystal lattice when there is more than one type of cation. It is known that the most prominent mechanism of charge transport in oxides is through hopping that follows the polaron models. But the polaron hopping models are too crude to account for the configurational differences that occur in ternary transition metal spinels, where the two different cation types can exhibit large degrees of disorder between the two cation lattice sites and possess a variety of oxidation states. As a consequence, the effects of cation disorder and cation oxidation states on electronic conductivity has not been well-described in multinary spinels. To investigate this question the team is synthesizing ternary oxide spinels, characterizing the cation disorder, and correlating the disorder with the electronic transport. The team is using x-ray emission spectroscopy, high-angle annular dark-field imaging, and electron energy loss spectroscopy to determine site occupancy, oxidation states, and local atomic segregation. The experimental results are coupled with theory to understand the mechanisms and outline a global model for transport. The team is using DFT-type calculations with periodic and non-periodic boundary conditions, and is analyzing charge transport characteristics related to hopping mechanisms in oxide materials to determine if the charge carriers lie on delocalized (overlapping) or localized states for specific cation distributions and concentrations. Understanding the fundamental mechanisms of polarons is a grand challenge for fields including molecular architectures, and electrical energy storage, where details of charge transport in poor electron-conductor materials could have a large impact. Understanding the relationship between cation configurational disorder and polaron hopping could lead to designer oxides with tailored properties. The team is promoting science to the public by creating a website with on-line training videos for international science outreach and to strengthen the US-Israel partnership using science for peaceful purposes, and designing an experiment on electronic conductivity in oxides for Lending Library Experiments.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.

非技术摘要：众所周知，氧化物是具有低电子电导率的材料。但经过仔细检查，他们的充电能力存在很大差异，其中大部分是无法解释的。例如，在钴锰氧化物中，电导率可增加多达 10 倍，具体取决于钴与锰的比例。当只有两种成分时，例如只有钴和氧，现有理论是准确的，但当包含第三种成分时，这些理论就崩溃了。在这个项目中，该团队正在研究氧化物的一个基本问题：原子无序如何影响氧化物的电导率。通过阐明这些机制，该团队正在开辟新的途径来定制氧化物的电导率，这对于依赖氧化物绝缘特性的应用（如半导体晶体管）或可以受益于电导率增加的应用（如电池和半导体）非常重要。燃料电池。为了向公众传播和推广科学，该团队正在创建一个包含在线培训视频的网站，以加强国际科学推广和美国与以色列的伙伴关系，利用科学用于和平目的，该团队正在设计一个关于氧化物中电子传导性的模块图书馆借阅实验。该套件符合特定的下一代科学标准，并使用探索性实践活动来帮助体验式学习。技术摘要：这项工作的目的是研究三元氧化物中的一个基本问题：当阳离子的类型不止一种。众所周知，氧化物中最重要的电荷传输机制是通过遵循极化子模型的跳跃。但极化子跳跃模型过于粗糙，无法解释三元过渡金属尖晶石中发生的构型差异，其中两种不同的阳离子类型可以在两个阳离子晶格位点之间表现出很大程度的无序性，并具有多种氧化态。因此，多元尖晶石中阳离子无序和阳离子氧化态对电子电导率的影响尚未得到很好的描述。为了研究这个问题，该团队正在合成三元氧化物尖晶石，表征阳离子无序，并将无序与电子传输相关联。该团队正在使用 X 射线发射光谱、高角度环形暗场成像和电子能量损失光谱来确定位点占用、氧化态和局部原子偏析。实验结果与理论相结合，以了解其机制并概述运输的全球模型。该团队正在使用具有周期性和非周期性边界条件的 DFT 类型计算，并分析与氧化物材料中的跳跃机制相关的电荷传输特性，以确定电荷载流子是否处于特定阳离子分布的离域（重叠）或局域状态，以及浓度。了解极化子的基本机制对于分子结构和电能存储等领域来说是一个巨大的挑战，在这些领域，不良电子导体材料中的电荷传输细节可能会产生很大的影响。了解阳离子构型无序和极化子跳跃之间的关系可能会导致设计具有定制特性的氧化物。该团队正在通过创建一个包含在线培训视频的网站来向公众宣传科学，以促进国际科学推广，并加强美国与以色列利用科学用于和平目的的伙伴关系，并为借阅图书馆实验设计氧化物中电子电导率的实验。该奖项反映了 NSF 的法定使命，并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，被认为值得支持。

项目成果

Enhanced Li-ion diffusion and electrochemical performance in strained-manganese–iron oxide core–shell nanoparticles

应变锰-氧化铁核-壳纳米粒子中增强的锂离子扩散和电化学性能

• DOI: 10.1063/5.0065506
• 发表时间: 2021-10
• 期刊: The Journal of Chemical Physics
• 作者: Bhargava, Anuj;Elbaz, Yuval;Sam, Quynh;Smeaton, Michelle A.;Kourkoutis, Lena F.;Caspary Toroker, Maytal;Robinson, Richard D.
• 通讯作者: Robinson, Richard D.

General Route to Colloidally Stable, Low-Dispersity Manganese-Based Ternary Spinel Oxide Nanocrystals

胶体稳定、低分散锰基三元尖晶石氧化物纳米晶体的一般途径

• DOI: 10.1021/jacs.3c05706
• 发表时间: 2023-08
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Rowell, Jonathan L.;Jia, Yafu;Shi, Zixiao;Molina Villarino, Andrés;Kang, Minsoo;Yoon, Dasol;Jiang, Kevin Zhijian;Abruña, Héctor D.;Muller, David A.;Robinson, Richard D.
• 通讯作者: Robinson, Richard D.

X-ray emission spectroscopy: an effective route to extract site occupation of cations

X射线发射光谱：提取阳离子位点占用的有效途径

• DOI: 10.1039/c8cp04628j
• 发表时间: 2018-11
• 期刊: Physical Chemistry Chemical Physics
• 影响因子: 3.3
• 作者: Bhargava, Anuj;Chen, Cindy Y.;Finkelstein, Kenneth D.;Ward, Matthew J.;Robinson, Richard D.
• 通讯作者: Robinson, Richard D.

Breakdown of the Small‐Polaron Hopping Model in Higher‐Order Spinels

高阶尖晶石中小极化子跳跃模型的分解

• DOI: 10.1002/adma.202004490
• 发表时间: 2020-10
• 期刊: Advanced Materials
• 影响因子: 29.4
• 作者: Bhargava, Anuj;Eppstein, Roni;Sun, Jiaxin;Smeaton, Michelle A.;Paik, Hanjong;Kourkoutis, Lena F.;Schlom, Darrell G.;Caspary Toroker, Maytal;Robinson, Richard D.
• 通讯作者: Robinson, Richard D.

Multiscale hierarchical structures from a nanocluster mesophase

纳米团簇中间相的多尺度分级结构

• DOI: 10.1038/s41563-022-01223-3
• 发表时间: 2022-04
• 期刊: Nature Materials
• 影响因子: 41.2
• 作者: Han, Haixiang;Kallakuri, Shantanu;Yao, Yuan;Williamson, Curtis B.;Nevers, Douglas R.;Savitzky, Benjamin H.;Skye, Rachael S.;Xu, Mengyu;Voznyy, Oleksandr;Dshemuchadse, Julia;et al
• 通讯作者: et al