Collaborative Research: Promoting Lithium Sulfides Redox Cycle via Atomically Dispersed Active Sites for Batteries

合作研究：通过电池的原子分散活性位点促进硫化锂氧化还原循环

• 批准号: 2129983
• 负责人: Zhaoyang Fan
• 金额: $ 34.98万
• 依托单位: Arizona State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-09-01 至 2025-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2129983&HistoricalAwards=false
• 关键词: Collaborative; Research; Promoting; Lithium; Sulfides

Batteries play a key role in information technology, energy storage, and reduction in carbon emissions. The lithium-sulfur battery uses earth-abundant sulfur as the cathode material and delivers more energy than the current batteries, thus it is considered as one of the next-generation technologies. However, its chemistry of converting between sulfur and lithium sulfides is a very complex process and has fundamental problems that result in low capacity and short battery lifetime, such as the dissolution of intermediate products and their shuttling between the two electrodes. Recent evidence has shown the critical role of single-atom catalysts in promoting this conversion process and subsequently boosting the battery performance, but the fundamental understanding of the active catalytic sites and the reaction mechanism remains very elusive. This hinders the development of a catalyst-functionalized cathode structure with much improved performance. The current project will fill this knowledge gap, thus accelerating the development of a practical lithium-sulfur battery technology to serve the national interest in the key energy storage applications. The project will also result in societal boarder impacts. The knowledge gained on single-atom catalysts can be applied to other electrochemical systems. Graduate and undergraduate students, including those from underrepresented groups, will be trained in the fields of advanced material science and battery technology. The research outcomes will be incorporated into the elective courses. The research teams will reach out to the local communities, recruiting high school students to conduct research and delivering public lectures on the new battery technology to local public libraries. This collaborative fundamental research project will attain theoretical understanding and experimental validation of the structure-property correlation of atomically dispersed catalysts in promoting lithium sulfides redox cycle, and to transform these understandings into an optimized sulfur cathode design. The project hypothesizes that the electronic structure of the single-atom catalyst, which is determined by both the metal center and its local coordination, can be tuned for binding polysulfides and activating the Li-S and S-S bonds with an optimized strength, thus significantly improving the landscape of sulfides conversion while preventing polysulfides shuttling. To this end, combining theoretical calculations and modeling with in-situ/ex-situ experimental studies, this project will establish the structure-property correlation of single-atom catalysts in chemisorbing polysulfides and activating the Li-S and S-S bonds for conversion, and probe and visualize the evolution of the electrode morphology and its chemical distribution during cycling. The studies will thus provide insights on the choice of the metal center, its local coordination, and the electrolyte in the proximity, and reveal their impacts on the lithium sulfides redox cycle. These understandings of single-atom catalyst functions on sulfides binding and conversion, both thermodynamically and kinetically, assisted by advanced characterization tools, will then be leveraged to design advanced sulfur cathode structures, functionalized with single-atom catalysts, for demonstration of battery cells with much-improved performance.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.

电池在信息技术、能源存储和减少碳排放方面发挥着关键作用。锂硫电池使用地球上丰富的硫作为正极材料，比现有电池提供更多的能量，因此被认为是下一代技术之一。然而，硫和硫化锂之间的化学转化是一个非常复杂的过程，并且存在导致容量低和电池寿命短的基本问题，例如中间产物的溶解及其在两个电极之间的穿梭。 最近的证据表明单原子催化剂在促进这种转化过程并随后提高电池性能方面发挥着关键作用，但对活性催化位点和反应机制的基本理解仍然非常难以捉摸。 这阻碍了性能大大提高的催化剂功能化阴极结构的开发。当前的项目将填补这一知识空白，从而加速实用锂硫电池技术的开发，以服务于关键能源存储应用的国家利益。该项目还将产生社会边界影响。在单原子催化剂上获得的知识可以应用于其他电化学系统。研究生和本科生，包括来自代表性不足群体的学生，将接受先进材料科学和电池技术领域的培训。研究成果将纳入选修课。 研究团队将深入当地社区，招募高中生进行研究，并向当地公共图书馆提供有关新型电池技术的公开讲座。该合作基础研究项目将获得对原子分散催化剂在促进硫化锂氧化还原循环中的结构-性能相关性的理论理解和实验验证，并将这些理解转化为优化的硫阴极设计。该项目假设，单原子催化剂的电子结构由金属中心及其局部配位决定，可以通过调整来结合多硫化物并以优化的强度激活Li-S和S-S键，从而显着提高硫化物转化的景观，同时防止多硫化物穿梭。为此，该项目将理论计算和建模与原位/非原位实验研究相结合，建立单原子催化剂在化学吸附多硫化物和激活Li-S和S-S键转化方面的结构-性能关联，以及探测并可视化循环过程中电极形态的演变及其化学分布。因此，这些研究将为金属中心的选择、其局部配位和附近的电解质提供见解，并揭示它们对硫化锂氧化还原循环的影响。这些对单原子催化剂在硫化物结合和转化方面的热力学和动力学功能的理解，在先进的表征工具的帮助下，将被用来设计先进的硫阴极结构，用单原子催化剂进行功能化，以演示具有多种功能的电池。 - 提高绩效。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

Fe-single-atom catalyst nanocages linked by bacterial cellulose-derived carbon nanofiber aerogel for Li-S batteries

用于锂硫电池的由细菌纤维素衍生的碳纳米纤维气凝胶连接的铁单原子催化剂纳米笼

• DOI: 10.1016/j.cej.2023.146977
• 发表时间: 2023-10
• 期刊: Chemical Engineering Journal
• 影响因子: 15.1
• 作者: Lin, Xueyan;Li, Wenyue;Nguyen, Vy;Wang, Shu;Yang, Shize;Ma, Lu;Du, Yonghua;Wang, Bin;Fan, Zhaoyang
• 通讯作者: Fan, Zhaoyang

Oxidized bacterial cellulose functionalized with SiO2 nanoparticles as a separator for lithium-metal and lithium–sulfur batteries

用 SiO2 纳米粒子功能化的氧化细菌纤维素作为锂金属和锂硫电池的隔膜

• DOI: 10.1007/s10570-022-04931-w
• 发表时间: 2023-01
• 期刊: Cellulose
• 影响因子: 5.7
• 作者: Li, Wenyue;Wang, Shu;Fan, Zhaoyang;Li, Shiqi;Newman, Nathan
• 通讯作者: Newman, Nathan

Biopolymer Separators from Polydopamine-Functionalized Bacterial Cellulose for Lithium-Sulfur Batteries

用于锂硫电池的聚多巴胺功能化细菌纤维素生物聚合物分离器

• DOI: 10.1016/j.jcis.2023.11.138
• 发表时间: 2023-11
• 期刊: Journal of Colloid and Interface Science
• 影响因子: 9.9
• 作者: Baranwal, Rishav;Lin, Xueyan;Li, Wenyue;Pan, Xuan;Wang, Shu;Fan, Zhaoyang
• 通讯作者: Fan, Zhaoyang

Electrocatalytic and Conductive Vanadium Oxide on Carbonized Bacterial Cellulose Aerogel for the Sulfur Cathode in Li-S Batteries

碳化细菌纤维素气凝胶上的电催化和导电氧化钒用于锂硫电池中的硫阴极

• DOI: 10.3390/batteries9010014
• 发表时间: 2023-01
• 期刊: Batteries
• 作者: Lin, Xueyan;Li, Wenyue;Pan, Xuan;Wang, Shu;Fan, Zhaoyang
• 通讯作者: Fan, Zhaoyang