Arrayed Heterostructures of MoS₂ Nanosheets Anchored TiN Nanowires as Efficient Pseudocapacitive Anodes for Fiber-Shaped Ammonium-Ion Asymmetric Supercapacitors

Abstract

Nonmetallic ammonium ions that feature high safety, low molar mass, and small hydrated radius properties have shown great advantages in wearable aqueous supercapacitors. The construction of high-energy-density flexible ammonium-ion asymmetric supercapacitors (AASCs) is promising but still challenging due to the lack of high-capacitance pseudocapacitive anodes. Herein, freestanding core-shell heterostructures supported on carbon nanotube fibers were designed by anchoring MoS₂ nanosheets on nanowires (MoS₂@TiN/CNTF) as anodes for AASCs. With contributions of abundant active sites and conspicuous synergistic effects of multiple components for arrayed heterostructure engineering, the developed MoS₂@TiN/CNTF anodes exhibit a specific capacitance of 1102.5 mF cm^-2 at 2 mA cm^-2. Theoretical calculations confirm the dramatic enhancement of the binding strength of ammonium ions on the MoS₂ shell layer at the heterostructure, where a built-in electric field exists to accelerate the charge transfer. By utilizing a MnO₂/CNTF cathode and NH₄Cl/poly(vinyl alcohol) (PVA) as a gel electrolyte, quasi-solid-state fiber-shaped AASCs were successfully constructed, achieving a specific capacitance of 351.2 mF cm^-2 and an energy density of 195.1 μWh cm^-2, outperforming most recently reported fiber-shaped supercapacitors. This work provides a promising strategy to rationally design heterostructure engineering of MoS₂@TiN nanoarrays toward advanced anodes for application in next-generation AASCs.