Liu Xiao, Liu Jingjing, Zhao Huijuan, Dong Chang, Liu Fengquan, Li Lin
College of Textiles & Clothing, State Key Laboratory of Bio-Fibers and Eco-Textiles, Qingdao University, Qingdao 266071, PR China.
College of Textiles & Clothing, State Key Laboratory of Bio-Fibers and Eco-Textiles, Qingdao University, Qingdao 266071, PR China.
J Colloid Interface Sci. 2025 Feb;679(Pt A):1106-1116. doi: 10.1016/j.jcis.2024.10.023. Epub 2024 Oct 9.
The electrochemical performance of lithium metal batteries (LMBs) was hampered by the uncontrolled growth of lithium (Li) dendrites. To address this issue, the extensive application of artificial solid electrolyte interphase (SEI) coatings on anode surfaces emerged as an effective solution. Electrospinning, as an innovative technique for fabricating artificial SEI layers on the surface of copper (Cu) foil, effectively mitigated Li volume strain during cycling. In this study, an electrospun organic-inorganic composite nanofiber membrane was in-situ fabricated on Cu foil, serving as an artificial SEI layer (CuWs) for anode-free LMBs (AF-LMBs) to enhance battery performance. Lithiophilic polyvinylpyrrolidone was used as the polymer matrix, and Cu nitrate served as the inorganic functional particles capable of in-situ redox reactions. The CuWs with their three-dimensional (3D) network structure accommodated electrode volume changes and suppressed Li dendrite growth during Li deposition and stripping. Additionally, CuWs facilitated the in-situ generation of Li nitrate (LiNO), which helped stabilize SEI layer and enhance Li utilization. The release sites of LiNO on the nanofibers enabled the in-situ reduction of metallic Cu, providing nucleation sites for Li deposition and forming the 3D ion-electron hybrid conductive networks. This CuWs layer reduced interfacial resistance and nucleation barriers, promoting uniform Li distribution on the anode surface. Li-Cu cells incorporating CuWs exhibited remarkable cycling stability, enduring over 460 cycles at 1.0 mA cm and 1.0 mAh cm with an average Coulombic efficiency of over 98.6 %. In Li-poor cells, the LFP|PE|CuWs achieved stable cycling for more than 30 cycles at 1.0 C, with a capacity retention rate of 92.0 %. These findings demonstrated that the CuWs membrane significantly enhanced the electrochemical performance of Li-poor cells and provided a novel artificial SEI protective strategy for advanced AF-LMBs with high energy density.
锂金属电池（LMBs）的电化学性能受到锂（Li）枝晶无控制生长的阻碍。为了解决这个问题，在阳极表面广泛应用人工固体电解质界面（SEI）涂层成为一种有效的解决方案。静电纺丝作为一种在铜（Cu）箔表面制备人工SEI层的创新技术，有效地减轻了循环过程中的锂体积应变。在本研究中，在铜箔上原位制备了一种静电纺丝有机-无机复合纳米纤维膜，作为无阳极LMBs（AF-LMBs）的人工SEI层（CuWs）以提高电池性能。亲锂的聚乙烯吡咯烷酮用作聚合物基体，硝酸铜用作能够进行原位氧化还原反应的无机功能颗粒。具有三维（3D）网络结构的CuWs能够适应电极体积变化，并在锂沉积和剥离过程中抑制锂枝晶生长。此外，CuWs促进了硝酸锂（LiNO）的原位生成，这有助于稳定SEI层并提高锂利用率。纳米纤维上LiNO的释放位点使得金属铜能够原位还原，为锂沉积提供成核位点并形成3D离子-电子混合导电网络。这个CuWs层降低了界面电阻和成核势垒，促进锂在阳极表面均匀分布。包含CuWs的锂-铜电池表现出显著的循环稳定性，在1.0 mA cm和1.0 mAh cm下可经受超过460次循环，平均库仑效率超过98.6%。在贫锂电池中，LFP|PE|CuWs在1.0 C下实现了超过30次循环的稳定循环，容量保持率为92.0%。这些发现表明，CuWs膜显著提高了贫锂电池的电化学性能，并为具有高能量密度的先进AF-LMBs提供了一种新型的人工SEI保护策略。
