CAS-Climate:Collaborative Research:Understanding How Electrochemical Cation Trapping in Metal Oxides Enhances Subsequent Reversible Insertion of Anions in Forming Metal Oxyhalides

CAS-气候：合作研究：了解金属氧化物中的电化学阳离子捕获如何增强随后形成金属卤氧化物时阴离子的可逆插入

• 批准号: 2221646
• 负责人: De-en Jiang
• 金额: $ 30万
• 依托单位: Vanderbilt University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-09-01 至 2026-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2221646&HistoricalAwards=false
• 关键词: CAS; Climate; Collaborative; Research; Understanding

Non-technical Abstract: Greater adoption of renewable energy sources necessitates economical and scalable electric-energy storage solutions. Novel battery chemistry holds the key to much-needed next-generation electric energy storage technologies to enable a sustainable society. Conventional batteries utilize cation-focused battery chemistry, which means positively charged ions migrate during the charge and discharge of a battery. With this project, supported by the Ceramics program in the Division of Materials Research, researchers at Oregon State University and Vanderbilt University investigate a possible mechanism for anion-based batteries (with migrating negatively charged ions instead of positively charged ones) for grid storage. Anion batteries have a great potential to replace current cation batteries for scalable energy storage, but fundamental mechanistic understanding is lacking. The project generates knowledge about what chemical environment in the metal-oxide battery material is more suitable for the transport and storage of anions during battery operation. Only sustainable, earth-abundant elements are investigated in the project for the electrodes, including manganese- and iron-based oxides, halide ions, and hydroxide; they are coupled with inexpensive and safe aqueous electrolytes. The new battery chemistry, if developed successfully, will greatly benefit our society by providing a low-cost, environmentally friendly energy-storage solution in the future. As part of the project the PIs introduce state-of-the-art materials research of novel battery chemistry to students from underserved communities and disseminate the knowledge to the public through institutional tools such as an online course.Technical Abstract:The knowledge of electrochemical anion insertion in hosts remains limited, particularly when the hosts are metal oxides. Anion insertion in metal oxides is inherently challenging because the interstitials are lined with oxides that repulse incoming anions. This project, supported by the Ceramics program in the Division of Materials Research, precisely tackles this problem by transforming the local structures of metal oxides with trapped cations. Researchers at Oregon State University and Vanderbilt University elucidate a new ion insertion mechanism whereby the irreversible insertion of cations in metal oxides promotes the reversible anion storage to form metal oxyhalides. Their research tests the central hypothesis that cation trapping transforms the structure of metal oxides and the chemical environment such that the subsequent anion insertion is greatly enhanced. They elucidate how the cation trapping alters the local structures of metal oxides and how the anions interact with the trapped cations and advance our understanding of the chemical environment and the changes caused by cation trapping and the anion insertion. Utilizing the synergy of expertise in electrochemical and structural characterization and first principles predictive modeling, the researchers establish mechanistic understandings of this new mechanism by investigating the model structure of spinel Mn3O4, in which the trapped Zn-ions enhances chloride storage. The project also develops a general principle of the new mechanism across different cations to be trapped, metal oxides as hosts, and anion charge carriers. Additionally, the integrated experimental and computation studies lay the foundation for a promising new research field using anion insertion to form metal oxyhalides.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：更多地采用可再生能源需要经济和可扩展的电能存储解决方案。新的电池化学是实现可持续社会所需的下一代电能存储技术的关键。传统电池采用以阳离子为中心的电池化学，这意味着正电荷离子在电池的充放电过程中迁移。在材料研究部陶瓷项目的支持下，俄勒冈州立大学和范德比尔特大学的研究人员研究了一种基于负离子的电池(使用迁移的负电荷离子而不是正电荷离子)用于栅极存储的可能机制。阴离子电池在可扩展储能方面有很大的潜力取代目前的阳离子电池，但缺乏基本的机理了解。该项目产生了关于金属氧化物电池材料中的哪些化学环境更适合在电池运行期间运输和存储负离子的知识。在该项目中，电极只研究了可持续的、富含地球的元素，包括锰基和铁基氧化物、卤离子和氢氧化物；它们与廉价和安全的水溶液结合在一起。新的电池化学如果开发成功，将在未来提供一种低成本、环保的储能解决方案，从而极大地造福于我们的社会。作为该项目的一部分，PIs向来自服务不足社区的学生介绍了新型电池化学的最新材料研究，并通过在线课程等机构工具向公众传播这些知识。技术摘要：关于在宿主中插入电化学阴离子的知识仍然有限，特别是当宿主是金属氧化物时。在金属氧化物中插入阴离子具有内在的挑战性，因为间隙中排列着排斥进入的阴离子的氧化物。该项目在材料研究部陶瓷项目的支持下，通过改变金属氧化物的局部结构来解决这个问题。俄勒冈州立大学和范德比尔特大学的研究人员阐明了一种新的离子插入机制，即阳离子在金属氧化物中的不可逆插入促进了可逆的阴离子存储形成金属氧卤化物。他们的研究验证了中心假设，即阳离子陷阱改变了金属氧化物的结构和化学环境，从而极大地增强了随后的阴离子插入。它们阐明了阳离子捕获如何改变金属氧化物的局域结构，以及阴离子如何与被捕获的阳离子相互作用，从而加深了我们对化学环境以及阳离子捕获和阴离子插入引起的变化的理解。利用电化学和结构表征方面的专业知识和第一性原理预测模型的协同作用，研究人员通过研究尖晶石Mn3O4的模型结构建立了对这一新机理的机理理解，其中捕获的锌离子增强了氯的储存。该项目还开发了新机制的一般原理，涉及要捕获的不同阳离子、作为主体的金属氧化物和阴离子电荷载流子。此外，综合的实验和计算研究为使用阴离子插入形成金属氧卤化物的有前景的新研究领域奠定了基础。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势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

Reversible Cl 2 /Cl – Redox for Low-Temperature Aqueous Batteries

用于低温水系电池的可逆 Cl 2 /Cl → 氧化还原

• DOI: 10.1021/acsenergylett.2c02757
• 发表时间: 2023
• 期刊: ACS Energy Letters
• 影响因子: 22
• 作者: Sui, Yiming;Lei, Ming;Yu, Mingliang;Scida, Alexis;Sandstrom, Sean K.;Stickle, William;O’Larey, Timothy D.;Jiang, De-en;Ji, Xiulei
• 通讯作者: Ji, Xiulei