Eu-viologen based bimetal–organic frameworks nanosheets with Mn atoms anchored on Eu-µ-O skeletons as high-performance negative electrode for flexible asymmetric supercapacitors

Exploring advanced negative electrode materials is imperative to develop high-performance asymmetric supercapacitors for breaking through current energy density limits of supercapacitors, but remains challenging. Herein, a strategy is proposed to create a novel negative electrode by anchoring Mn single-atoms on Eu-viologen metal–organic frameworks (EV-Mn MOFs) nanosheets flowery architectures that self-supported on oxidized carbon cloths (OCC). Such EV-Mn/OCC achieves a negative broadened voltage window (−1 ∼ 0 V) and boosted areal capacitance (840.82 mF cm−2), which is four folds of the isostructural EV/OCC without Mn atoms and surpasses most of currently reported negative electrodes. Also, the EV-Mn/OCC manifests good cycling stability (∼80 % retention for 10,000 cycles). As deduced by the thorough studies of X-ray absorption fine spectra and X-ray photoelectron spectroscopies, the enhanced pseudocapacitance of EV-Mn/OCC definitely correlates to the valence modulation of Mn and Eu through internal electron transfer via Eu-O-Mn bonds on Eu-µ-O skeleton in EV-Mn MOFs. Subsequently, the constructed flexible all-solid-state symmetric supercapacitors employing EV-Mn/OCC as negative electrode can deliver a high energy density (86.89 μWh cm−2) at 1600 μW cm−2, outperforming many asymmetric devices based on traditional negative electrode materials. This work can spur the development of single-atom metallic electronic-modulation strategy for MOFs negative electrode material (MOFs-NEM), and accelerate their applications in flexible energy conversion and storage devices.