Mou Yujin, Yang Hongyan, Lang Yunjie, Sun Lanju, Wang Xiao, Deng Wei-Qiao, Wu Hao
Institute of Frontier Chemistry, School of Chemistry and Chemical Engineering, Shandong University, Qingdao 266237, China.
College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University, Qingdao 266109, China.
J Colloid Interface Sci. 2025 Dec;699(Pt 2):138269. doi: 10.1016/j.jcis.2025.138269. Epub 2025 Jun 23.
Conventional sodium-ion battery (SIB) anodes are still lagging in capacity, reaction kinetics, and cycling stability, which motivates the development of high-performance anodes for advancing grid-scale energy storage. Herein, we report a ferrocene-based metal-organic framework (NF-MOF) anode with dual redox sites, synthesized on carbon cloth (CC) via a facile solvothermal method. This innovative design yields a binder-free NF-MOF@CC anode that integrates the redox activity of ferrocene (Fc/Fc) with the Ni/Ni redox couple. The prudent design ensures intimate interfacial contact between NF-MOF and CC, eliminating binder-induced resistance and accommodating Na-induced strain through hierarchical porosity. As a result, NF-MOF@CC shows rapid capacitive-dominated Na storage and high diffusion coefficients, delivering a high reversible capacity of 705 mAh g at 0.1 A g and achieving a 3.9-time higher capacity than its powder counterpart. Ex situ structural and simulation studies confirm reversible Ni and Fe redox reactions with minimized lattice distortion, while electrostatic potential mapping identifies optimal Na adsorption sites. Moreover, full-cell configurations paired with NaV(PO) or NaNiFeMnO cathodes achieve remarkable cyclability, retaining 95.1 % (200th cycle) and 95.3 % (500th cycle) capacity, respectively, alongside high energy densities (310 Wh kg at 3160 W kg). This work pioneers a dual-redox MOF design strategy, offering a universal platform for robust, high-capacity SIB anodes.
传统钠离子电池（SIB）的负极在容量、反应动力学和循环稳定性方面仍存在不足，这推动了高性能负极的开发，以推进电网规模的储能应用。在此，我们报道了一种基于二茂铁的金属有机框架（NF-MOF）负极，其具有双氧化还原位点，通过简便的溶剂热法在碳布（CC）上合成。这种创新设计产生了一种无粘结剂的NF-MOF@CC负极，它将二茂铁（Fc/Fc）的氧化还原活性与Ni/Ni氧化还原对相结合。精心设计确保了NF-MOF与CC之间的紧密界面接触，消除了粘结剂引起的电阻，并通过分级孔隙率适应钠诱导的应变。结果，NF-MOF@CC表现出快速的电容主导型钠存储和高扩散系数，在0.1 A g下提供705 mAh g的高可逆容量，比其粉末对应物的容量高3.9倍。非原位结构和模拟研究证实了可逆的Ni和Fe氧化还原反应，晶格畸变最小，而静电势映射确定了最佳的钠吸附位点。此外，与NaV(PO)或NaNiFeMnO正极配对的全电池配置具有出色的循环稳定性，分别在第200次循环和第500次循环时保留95.1%和95.3%的容量，同时具有高能量密度（在3160 W kg时为310 Wh kg）。这项工作开创了一种双氧化还原MOF设计策略，为坚固、高容量的SIB负极提供了一个通用平台。
