Phosphorus-Functionalized Organic Linkers Promote Polysulfide Retention in MOF-Based Li–S Batteries
Phosphorus-Functionalized Organic Linkers Promote Polysulfide Retention in MOF-Based Li–S Batteries
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DOI：
10.1021/acsaem.2c02925
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发表时间：
2022-11
影响因子：
6.4
通讯作者：
Avery E. Baumann;Rasha I. Anayah;V. S. Thoi
中科院分区：
文献类型：
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作者：
Avery E. Baumann;Rasha I. Anayah;V. S. Thoi
金属有机框架（MOF）因其高孔隙率和合成可调性而成为热门研究领域，这为它们提供了适合各种应用的可控物理和化学性质。在这项研究中，我们证明功能化 MOF 可用于减轻锂硫电池中所谓的多硫化物穿梭效应，锂硫电池是一种有前途的下一代储能设备。 UiO-66-OH 是一种含有 2-羟基对苯二甲酸的锆基 MOF，用氯化磷物质进行功能化，随后用于束缚多硫化物。此外，还合成了分子氯正膦作为模型系统，以阐明磷部分的化学反应性。然后将功能化的 MOF 用作纽扣电池中的阴极添加剂，以抑制多硫化物在溶液中的溶解。通过这项工作，我们表明，MOF 与磷的功能化增强了多硫化物的氧化还原，从而增强了 Li-S 电池的容量保持能力。虽然此处展示了电池中的多硫化物束缚，但我们预计这种连接体功能化策略可以更广泛地应用于分离、传感或催化应用。
Metal–organic frameworks (MOFs) have been an area of intense research for their high porosity and synthetic tunability, which afford them controllable physical and chemical properties for various applications. In this study, we demonstrate that functionalized MOFs can be used to mitigate the so-called polysulfide shuttle effect in lithium–sulfur batteries, a promising next-generation energy storage device. UiO-66-OH, a zirconium-based MOF with 2-hydroxyterephthalic acid, was functionalized with a phosphorus chloride species that was subsequently used to tether polysulfides. In addition, a molecular chlorophosphorane was synthesized as a model system to elucidate the chemical reactivity of the phosphorus moiety. The functionalized MOFs were then used as a cathode additive in coin cell batteries to inhibit the dissolution of polysulfides in solution. Through this work, we show that the functionalization of MOF with phosphorus enhances polysulfide redox and thereby capacity retention in Li–S batteries. While demonstrated here for polysulfide tethering in batteries, we envision this linker functionalization strategy could be more broadly utilized in separations, sensing, or catalysis applications.