新型纳米裂纹结构隔膜的设计及其在锂离子电池中的应用

Design of novel nanocrack-structured separators and their application in lithium-ion batteries

  • 摘要: 隔膜是电池的关键组件,能够提供离子传输通道并防止正负极接触短路,对储能系统的稳定运行至关重要. 目前商业化锂离子电池隔膜主要通过干法和湿法工艺生产,尽管各类二次电池技术发展迅猛,但高端隔膜技术仍依赖进口,成为制约储能产业发展的瓶颈,开发高性能隔膜已成为当前研究的重中之重. 传统湿法隔膜制备工艺的隔膜孔径分布和孔隙率可控,但其需大量使用洗脱溶剂,导致能耗高、工艺复杂且成本较高. 本工作提出一种利用聚对苯二甲酸–己二酸丁二醇酯(PBAT)和等规聚丙烯(IPP)的相容性差异,采用简单的熔融共混–吹塑工艺实现聚合物微相分离,构建形成具有均匀的纳米裂纹结构的新型电池隔膜以实现离子传输(离子传导率达0.25 mS·cm−1). 该隔膜制备工艺省去传统湿法和干法隔膜工艺中的造孔步骤(溶剂洗脱或拉伸定型工序),显著提升生产效率并降低能耗. 所制备隔膜表现出优异力学性能,横、纵向极限拉伸强度分别为7.52 MPa和21.74 MPa,应变高达392.41%和597.58%. 组装Li//LiFePO4电池后,在0.1 C电流密度下首周放电比容量达155.99 mA·h·g−1,循环100次后容量保持率为92.9%,验证了该工艺的可行性. 该研究为新型电池隔膜设计与工艺研发提供了新的思路.

     

    Abstract: The separator, which provides an ion transport pathway while preventing short circuits between electrodes, is an essential component of secondary metal batteries and plays a pivotal role in the stable operation of energy storage systems. Currently, commercial lithium-ion battery separators are primarily prepared using dry and wet methods. Despite rapid advancements in various secondary energy storage systems, the domestic high-end separator market remains heavily reliant on imports, posing a bottleneck to the development of the energy storage industry. This dependence is due to not only the quality of raw materials but also the lack of precision separator production equipment. Consequently, developing high-performance separators based on new materials and preparation technologies has become a top priority in current research. Although traditional wet-process separator fabrication offers controllable pore size distribution and porosity, it requires extensive use of extraction solvents, leading to high energy consumption, complex procedures, and elevated costs. The dry process demands high-quality raw materials and involves complex production steps, increasing costs and production difficulty. According to the principle of similar compatibility, polymers with different polarities generally exhibit poor compatibility. Phase separation can form an interphase between polymers with significant polarity differences. Inevitably, weak interactions near this interphase result in a loose structure that allows ion transport. Abundant interphases can form sufficient ion channels for migration between the cathode and anode. Herein, owing to the insufficient compatibility of poly(butylene adipate-co-terephthalate) (PBAT) and isostatic polypropylene (IPP), we developed a novel nanocrack-structured separator with uniform microphase separation by blending via the blow molding process, enabling efficient ion transport with an ionic conductivity of 0.25 mS·cm−1. In traditional wet processes, pore-making involves the elution of pore-forming agents with bulk organic solvents and drying steps. The heat drawing and cooling parameters play key roles in forming long, narrow pore morphologies in the dry process. In comparison, the new preparation technology for nanocrack-structured separators is simple and mature, omitting the pore-making step. Furthermore, this low-equipment-cost process is suitable for large-scale production. The abundant nanocracks at the polymer interfaces maintain sufficient ion transport flux for normal charge-discharge processes. This method significantly enhances production efficiency while reducing energy consumption. Moreover, the prepared separator demonstrates superior mechanical properties, with transverse and longitudinal ultimate tensile strengths of 7.52 MPa and 21.74 MPa, respectively, and strains reaching 392.41% and 597.58%. The excellent ion conductivity and mechanical properties of the nanocrack-structured separator satisfy battery separator requirements. When assembled into Li//LiFePO4 batteries, the battery delivers an initial discharge capacity of 155.99 mA·h·g−1 at a current density of 0.1 C, with 92.9% capacity retention after 100 cycles, validating the application feasibility of this nanocrack-structured separator and preparation process. This study successfully eliminates the pore-forming step typical in traditional separator preparation, achieving dual benefits of reduced energy consumption and environmental protection. Furthermore, it innovatively utilizes nanocrack structures for ion transport, expanding applications in electrochemical energy storage and providing novel insights for advancing battery separator fabrication technologies.

     

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