Surface Engineered and Highly Redox Active Polar Oxide Host Materials Immobilizing Lithium Polysulfides for Long-Life and High-Performance Li-S Batteries

表面工程和高氧化还原活性极性氧化物主体材料固定多硫化锂，用于长寿命和高性能锂硫电池

• 批准号: 2118784
• 负责人: Ruigang Wang
• 金额: $ 34.53万
• 依托单位: University of Alabama Tuscaloosa
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-08-01 至 2024-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2118784&HistoricalAwards=false
• 关键词: Surface; Engineered; Highly; Redox; Active

Electrical energy storage is one of the most critical needs in power systems for a more sustainable future. Lithium–sulfur (Li-S) batteries are promising candidates because of their higher energy density and reduced cost due to the use of sulfur. However, a key limitation of the Li-S system is polysulfide shuttling. Shuttling occurs when polysulfide molecules from the cathode dissolve into the electrolyte and shuttle across the separator to react with the anode materials. This process is irreversible and leads to a rapidly fading capacity. This project addresses the fundamental shuttle effect of lithium polysulfides in lithium sulfur batteries with emphasis on developing surface engineered host materials for immobilizing lithium polysulfides and promoting their conversion. A series of surface engineered and shape-controlled cerium oxides will be developed and characterized to understand which structural features best limit polysulfide shutting. Such knowledge is critical for designing novel host materials and long-life energy storage systems, which will have a potentially immense impact on portable electronics, electric vehicles, and devices for intermittent renewable energy storage from solar and wind resources. The investigator will continue to support the outstanding recruitment, mentoring, and retention of minority students in STEM by providing unique research opportunities for undergraduates as early as their freshman year and with continuing scholarships to promote their retention.The overall objective of this proposal is to elucidate the effect of surface engineered polar CeO2 addition as a host material via shape control (nanorods, nanocubes, and nanoctahedra with different exposed crystal planes: (110), (100) and (111)) and chemical etching treatment on the lithium polysulfides immobilization, catalytic conversion, and electrochemical performance in lithium-sulfur batteries. These findings will provide insight into a fundamental understanding of sulfur conversion chemistry and act as a guide for the future design and screening of new host materials toward achieving high sulfur loading/utilization in lithium-sulfur batteries. The investigators hypothesize that physical confinement and surface engineered polar CeO2 with distinct termination surface structures would effectively store and entrap sulfur species to prevent the dissolution and migration of intermediate lithium polysulfides avoiding the shuttle effect and capacity degradation during the electrochemical cycling. In addition, ex situ/in situ transmission electron microscopy and electron energy loss spectroscopy characterization techniques will be employed to achieve a deeper understanding of dynamic adsorption/desorption, liquid/solid and solid/solid interactions, and structural/compositional changes at the lithium polysulfides/CeO2 interface. New insights (quantitative dynamic atomic-level structural and chemical characterizations) into lithium polysulfides/CeO2 interfacial structures will provide powerful practical strategies to promote or suppress various kinds of interface phenomena. The obtained knowledge on battery chemistry of sulfur-oxide additive interaction promises long-life and high energy/power density lithium-sulfur batteries.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.

为了实现更可持续的未来，电能存储是电力系统中最关键的需求之一。锂硫（li -硫）电池因其更高的能量密度和由于使用硫而降低的成本而成为有希望的候选者。然而，Li-S系统的一个关键限制是多硫化物穿梭。当来自阴极的多硫化物分子溶解到电解液中并穿过分离器与阳极材料发生反应时，就会发生穿梭。这个过程是不可逆的，会导致能力迅速衰退。本项目主要研究多硫化物锂在硫锂电池中的基本穿梭效应，重点是开发用于固定多硫化物锂并促进其转化的表面工程主体材料。一系列表面工程和形状控制的铈氧化物将被开发和表征，以了解哪种结构特征最能限制多硫化物关闭。这些知识对于设计新型宿主材料和长寿命能量存储系统至关重要，这将对便携式电子产品，电动汽车以及太阳能和风能资源的间歇性可再生能源存储设备产生潜在的巨大影响。研究者将通过为本科生提供独特的研究机会，并提供持续的奖学金来提高他们的保留率，继续支持优秀的STEM少数民族学生的招聘、指导和保留。本研究的总体目标是阐明通过形状控制（纳米棒、纳米立方体和具有不同暴露晶体平面的纳米八面体：（110）、（100）和（111））和化学蚀刻处理，表面工程极性CeO2添加作为主体材料对锂硫电池中多硫化物锂的固定化、催化转化和电化学性能的影响。这些发现将提供对硫转化化学的基本理解，并作为未来设计和筛选新主体材料的指南，以实现锂硫电池的高硫负载/利用率。研究人员假设，物理约束和具有不同终端表面结构的表面工程极性CeO2可以有效地储存和捕获硫，以防止中间多硫化物锂的溶解和迁移，避免电化学循环过程中的穿梭效应和容量下降。此外，将采用非原位/原位透射电子显微镜和电子能量损失谱表征技术，以更深入地了解锂多硫化物/CeO2界面的动态吸附/解吸，液/固和固/固相互作用以及结构/组成变化。对多硫化锂/CeO2界面结构的新见解（定量动态原子级结构和化学表征）将为促进或抑制各种界面现象提供强大的实用策略。硫氧化物添加剂相互作用的电池化学知识为长寿命和高能量/功率密度的锂硫电池提供了希望。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识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

High-performance Li-S batteries enabled by polysulfide-infiltrated free-standing 3D carbon cloth with CeO2 nanorods decoration

• DOI: 10.1016/j.electacta.2021.138645
• 发表时间: 2021-08
• 期刊: Electrochimica Acta
• 影响因子: 6.6
• 作者: Zhen Wei;Junhao Li;Yifan Wang;Ruigang Wang

Cerium oxide nanorods anchored on carbon nanofibers derived from cellulose paper as effective interlayer for lithium sulfur battery

• DOI: 10.1016/j.jcis.2022.01.161
• 发表时间: 2022-02-08
• 期刊: JOURNAL OF COLLOID AND INTERFACE SCIENCE
• 影响因子: 9.9
• 作者: Azam, Sakibul;Wei, Zhen;Wang, Ruigang
• 通讯作者: Wang, Ruigang

Surface engineered polar CeO2-based cathode host materials for immobilizing lithium polysulfides in High-performance Li-S batteries

• DOI: 10.1016/j.apsusc.2021.152237
• 发表时间: 2022-04-01
• 期刊: APPLIED SURFACE SCIENCE
• 影响因子: 6.7
• 作者: Wei, Zhen;Li, Junhao;Wang, Ruigang
• 通讯作者: Wang, Ruigang