利用氢氟酸清除分离器通过界面氢键效应稳定高镍阴极

IF 10.1 1区 工程技术 Q1 ENGINEERING, MULTIDISCIPLINARY Engineering Pub Date : 2024-08-01 DOI:10.1016/j.eng.2023.09.025
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引用次数: 0

摘要

富镍层状锂过渡金属氧化物是最有希望用于高能量密度锂离子电池的正极材料。然而,由于过渡金属的溶解和结构重构,以及六氟磷酸锂分解产生氢氟酸(HF),它们的容量会迅速下降。工作过程中可能出现的热失控是另一个挑战。分离器是有望缓解上述障碍的元件。本文结合非溶剂诱导相反转工艺和涂层方法,设计并制造了一种超薄双层分离器,其基底层为 10 μm 的聚酰亚胺(PI),涂层层为 2 μm 的聚偏二氟乙烯(PVDF)。PI 骨架对潜在的热收缩具有良好的稳定性,PI-PVDF 的牢固粘合赋予了复合分离器坚固的结构完整性;这些特性共同造就了分离器在高温下非凡的机械耐受性。此外,由于亚胺环提供了丰富的高频配位位点,形成了-CO--H-F氢键,从而实现了独特的高频清除效应;因此,层状富镍阴极免受高频侵蚀,最终减少了过渡金属溶解,促进了富镍阴极的长期循环性。采用所提议的复合隔膜的镍钴锰酸锂 811 电池(其中 "NCM "表示镍钴锰酸锂 1-x-yO2)在室温下循环 400 次后容量保持率为 90.6%,在 60 °C、循环 200 次后容量保持率为 91.4%。本研究从分离器的新视角出发,提出了一种可行且前景广阔的策略,可用于抑制容量衰减,实现富镍阴极材料的安全运行。
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Stabilizing High-Nickel Cathodes via Interfacial Hydrogen Bonding Effects Using a Hydrofluoric Acid-Scavenging Separator

Nickel-rich layered Li transition metal oxides are the most promising cathode materials for high-energy-density Li-ion batteries. However, they exhibit rapid capacity degradation induced by transition metal dissolution and structural reconstruction, which are associated with hydrofluoric acid (HF) generation from lithium hexafluorophosphate decomposition. The potential for thermal runaway during the working process poses another challenge. Separators are promising components to alleviate the aforementioned obstacles. Herein, an ultrathin double-layered separator with a 10 μm polyimide (PI) basement and a 2 μm polyvinylidene difluoride (PVDF) coating layer is designed and fabricated by combining a non-solvent induced phase inversion process and coating method. The PI skeleton provides good stability against potential thermal shrinkage, and the strong PI–PVDF bonding endows the composite separator with robust structural integrity; these characteristics jointly contribute to the extraordinary mechanical tolerance of the separator at elevated temperatures. Additionally, unique HF-scavenging effects are achieved with the formation of –CO···H–F hydrogen bonds for the abundant HF coordination sites provided by the imide ring; hence, the layered Ni-rich cathodes are protected from HF attack, which ultimately reduces transition metal dissolution and facilitates long-term cyclability of the Ni-rich cathodes. Li||NCM811 batteries (where “NCM” indicates LiNixCoyMn1−xyO2) with the proposed composite separator exhibit a 90.6% capacity retention after 400 cycles at room temperature and remain sustainable at 60 °C with a 91.4% capacity retention after 200 cycles. By adopting a new perspective on separators, this study presents a feasible and promising strategy for suppressing capacity degradation and enabling the safe operation of Ni-rich cathode materials.

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来源期刊
Engineering
Engineering Environmental Science-Environmental Engineering
自引率
1.60%
发文量
335
审稿时长
35 days
期刊介绍: Engineering, an international open-access journal initiated by the Chinese Academy of Engineering (CAE) in 2015, serves as a distinguished platform for disseminating cutting-edge advancements in engineering R&D, sharing major research outputs, and highlighting key achievements worldwide. The journal's objectives encompass reporting progress in engineering science, fostering discussions on hot topics, addressing areas of interest, challenges, and prospects in engineering development, while considering human and environmental well-being and ethics in engineering. It aims to inspire breakthroughs and innovations with profound economic and social significance, propelling them to advanced international standards and transforming them into a new productive force. Ultimately, this endeavor seeks to bring about positive changes globally, benefit humanity, and shape a new future.
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