Dual-Functional Template-Induced In Situ Polymerization Process Enables the Hierarchical Carbonaceous Nanotubes with Simultaneous Sn Cluster Incorporation and Nitrogen-Doping for Superior Potassium-Ion Storage

Potassium ion-based energy storage devices have received extensive attention for grid-level applications due to their abundant natural resources and low cost. However, the large ionic radius of K+ leads to inferior capacities and cyclic stability, which hinders their practical application. Herein, hierarchical carbonaceous nanotubes with simultaneous ultrasmall Sn cluster incorporation and nitrogen doping (denoted as u-Sn@NCNTs) are fabricated using MnO2 nanowires as a dual-functional template (in situ polymerization and shape-directing agents) and subsequent carbonization treatment. The u-Sn@ NCNTs exhibit a superior K+ storage capability with a high reversible capacity (220.1 mA h g(-1) at 0.1 A g(-1)) and long cycling stability (149.9 mA h g(-1) at 1 A g(-1) after 4000 cycles). Besides, the u-Sn@NCNTs exhibit superior cycling stability up to 10000 cycles at 5 A g(-1) for Na+ storage. The potassium storage mechanism and kinetics are investigated based on ex situ X-ray photoelectron spectroscopy, in situ Raman spectrum, and galvanostatic intermittent titration technique. More importantly, u-Sn@NCNTs can be used as the anode for potassium ion hybrid capacitors, achieving a superior energy density of 181.4 W h kg(-1) at a power density of 185 W kg(-1) with excellent cycling capability. This work could push forward the development and application of carbonaceous-based anode materials for next-generation high-performance rechargeable batteries.

Automated summary

Hierarchical carbonaceous nanotubes incorporating ultrasmall Sn clusters and nitrogen doping (u-Sn@NCNTs) were successfully synthesized as high-performance anode materials for potassium ion-based energy storage devices. The u-Sn@NCNTs exhibited superior K+ storage capability with high reversible capacity and cycling stability, showing great potential for practical applications in grid-level energy storage systems.