Improved Capacitive Behavior of Birnessite Type Mn Oxide Coated on Activated Carbon Fibers

Birnessite type Mn oxide (potassium birnessite hydrate) powder (as-δ-MnO2) with a layered microstructure was prepared via a hydrothermal process. To improve its capacitive performance, the microstructure was thermally modified (annealed) at 400 oC (400-δ-MnO2) in a N2 reducing environment. By removing the hydrated cations (K+) layers inserted between the main layers of birnessite, damaging the microstructure, intercalation/deintercalation of the electrolyte species (Li+1) became more effective. Characterization of as-δ-MnO2 and 400-δ-MnO2 revealed that no phase transformation occurred during the annealing process. The microstructure became less crystalline and the total pore volume increased from 0.20 cm3 g-1 to 0.43 cm3 g-1, while the oxidation state of Mn remained 4+ after annealing the as-δ-MnO2 at 400 oC. The 400-δ-MnO2 sample was then coated on asphaltene derived activated carbon fibers (ACF-400-δ-MnO2) to improve the performance by making use of the high electrical conductivity and capacitive behavior of ACF. Coating the 400-δ-MnO2 sample led to a significant increase in the capacitance (328 F g-1 and 195 F g-1 for ACF-400-δ-MnO2 and 400-δ-MnO2 at 0.4 A g-1, respectively), improved energy and power values (~7 kW kg-1 at ~4.2 Wh kg-1 for ACF-400-δ-MnO2 and 240 W kg-1 at 2.4 Wh kg-1 for 400-δ-MnO2) and improved cycling behavior.