Establishing Hybrid Electrode Frameworks via Hierarchical Integration of MOFs and Conducting Polymers for Multidimensional Redox Synergy

Abstract Herein, a hierarchical hybrid electrode consisting of multidimensional PANI: PSS/Fe‐BTC/carbon fiber cloth (mPFC) is fabricated via the in situ growth of 2D BTC metal–organic framework (MOF) nanosheets on Fe‐electrodeposited carbon cloth and subsequent polymerization of PANI: PSS. The resulting architecture provides a mechanically robust electrode framework in which multiscale structural domains are seamlessly integrated. Such structural integration ensures strong interfacial coupling, continuous ion/electron transport pathways, and accelerated charge‐transfer kinetics. In particular, the incorporation of PANI: PSS introduces a dual redox‐active structure, thereby maximizing the exposure of electrochemically active sites throughout the electrode. As a result, the mPFC electrode delivers a high reversible capacity of 415 mA h g ⁻¹ at 0.1 A g ⁻¹ and retains 92.2% of its capacity after 3000 cycles at 2.0 A g ⁻¹ , along with an energy density of 275.2 W h kg ⁻¹ and a peak power density of 91.7 kW kg ⁻¹ . Experimental results accompanied by theoretical calculations verify that Fe‐BTC and PANI: PSS function as redox‐active sites for the storage of Li cations and PF ₆ anions, respectively, and that the low diffusion energy barrier (≈0.059 eV) enables the consecutive faradaic reactions of the mPFC electrode within a wide potential window of 2.0–4.5 V.