In-Situ Formation of Ternary Sulfide-rich Interphases for Stabilizing Lithium Deposition in Lithium-sulfur Batteries

原位形成富含三元硫化物的界面相以稳定锂硫电池中的锂沉积

基本信息

批准号：
2011415
负责人：
Arumugam Manthiram
金额：
$ 44.73万
依托单位：
University of Texas at Austin
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2020
资助国家：
美国
起止时间：
2020-07-01 至 2024-06-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2011415&HistoricalAwards=false
关键词：
Situ Formation Ternary Sulfide rich

项目摘要

Energy storage at an affordable cost has emerged as one of the challenging issues for the energy sector, being critical for a wide range of applications ranging from electric vehicles to grid storage of renewable energies. Lithium-sulfur batteries are one the most promising next-generation battery technologies, as lithium and sulfur exhibit charge-storage capacity ten times higher than that of the electrode materials used in current lithium-ion batteries. Also, sulfur is environmentally benign, inexpensive, and widely available with secure domestic supply chains. Despite these advantages, the commercial adoption of lithium-sulfur batteries is hobbled by their poor cycle life. This project focuses on developing an effective strategy for improving the cycle life of lithium-sulfur batteries by systematically tuning the surface composition and properties of the anode. The effect of the modified interface material anode layer on the cycle life will be investigated with various computational, electrochemical, and materials characterization techniques. This will be a crucial step towards realizing practically relevant lithium-sulfur batteries with high energy density and extended cycle life. This work is also expected to yield new insights into the unique chemistry of sulfur compounds, which find applications in diverse areas, including photovoltaics, catalysis, and organic semiconductors. The project will also provide a broad interdisciplinary training to graduate and undergraduate students as well as historically underrepresented community college students and teachers in the globally important area of clean energy, encompassing inorganic chemistry, solid-state physics, electrochemical systems, and materials science and engineering.The unique chemistry of sulfur and its tendency to form polysulfide intermediates that are soluble in the liquid electrolyte profoundly impact the solid-electrolyte interphase (SEI) layer formed on lithium-metal surface in Li-S batteries. This project focuses on developing a systematic and effective strategy for tailoring the composition of the SEI layer to improve the reversibility of lithium plating and stripping in Li-S batteries. Electrolyte and cathode additives will be identified that work in tandem with the generated polysulfide intermediates to form a stabilizing SEI layer on lithium-metal surface. Specifically, high Li-ion conductivity LiXS ternary sulfides will be investigated as in-situ engineered SEI components, where X is a high-oxidation state cation of an element less electronegative than sulfur. It is hypothesized that the nature of X-S bond would play a critical role in determining the properties of the modified SEI layer, and consequently, the measured lithium cycling efficiency. The impact of the in-situ modified SEI layers on electrochemical performance will be assessed with practically relevant anode-free full cells (limited lithium inventory) and pouch cells (limited electrolyte supply) by determining the lithium inventory loss rates. With the in-situ engineering of a sulfide-rich lithium SEI and careful application of computational and materials characterization techniques, the project aims to (i) identify stabilizing SEI components in Li-S batteries and methods of fabricating them, (ii) establish a fundamental understanding of the composition-structure-property relationships that underlie the effect of SEI layer on the reversibility of lithium plating and stripping, and (iii) demonstrate the impact of SEI modification on electrochemical performance under realistic cell design and testing conditions.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.

以可承受的成本进行能源存储已成为能源行业面临的挑战性问题之一，对于从电动汽车到可再生能源电网存储等广泛应用至关重要。锂硫电池是最有前途的下一代电池技术之一，因为锂和硫的电荷存储容量比当前锂离子电池中使用的电极材料高十倍。此外，硫对环境无害，价格低廉，并且可以通过安全的国内供应链广泛获得。尽管具有这些优点，但锂硫电池的商业应用因其较差的循环寿命而受到阻碍。该项目的重点是开发一种有效的策略，通过系统地调整阳极的表面成分和性能来提高锂硫电池的循环寿命。改性界面材料阳极层对循环寿命的影响将通过各种计算、电化学和材料表征技术进行研究。这将是实现具有高能量密度和延长循环寿命的实用锂硫电池的关键一步。这项工作还有望对硫化合物的独特化学产生新的见解，从而在光伏、催化和有机半导体等多个领域找到应用。该项目还将为全球重要的清洁能源领域的研究生和本科生以及历史上代表性不足的社区学院学生和教师提供广泛的跨学科培训，包括无机化学、固态物理、电化学系统以及材料科学与工程硫的独特化学性质及其形成可溶于液体电解质的多硫化物中间体的倾向，深刻影响了锂硫电池中锂金属表面形成的固体电解质界面（SEI）层。该项目的重点是开发一种系统且有效的策略来调整SEI层的成分，以提高锂硫电池中锂沉积和剥离的可逆性。电解质和阴极添加剂将与生成的多硫化物中间体协同作用，在锂金属表面形成稳定的 SEI 层。具体来说，高锂离子电导率的 LiXS 三元硫化物将作为原位工程 SEI 组分进行研究，其中 X 是电负性低于硫的元素的高氧化态阳离子。据推测，X-S 键的性质在确定改性 SEI 层的性能以及测量的锂循环效率方面将发挥关键作用。原位改性 SEI 层对电化学性能的影响将通过确定锂库存损失率，使用实际相关的无阳极全电池（有限的锂库存）和软包电池（有限的电解质供应）进行评估。通过富硫化物锂 SEI 的原位工程以及计算和材料表征技术的仔细应用，该项目旨在 (i) 确定 Li-S 电池中的稳定 SEI 成分及其制造方法，(ii) 建立对 SEI 层对锂沉积和剥离可逆性影响的成分-结构-性能关系的基本理解，以及 (iii) 证明 SEI 改性在实际电池设计和测试条件下对电化学性能的影响。该奖项反映了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，NSF 的法定使命被认为值得支持。