Performance of manganese oxide/CNTs composites as electrode materials for electrochemical capacitors

Nanocrystalline metal oxides can be prepared with large surface area, electrochemical stability, and pseudocapacitive behavior, being able to be used as supercapacitor electrodes. Among the various metal oxides studied, amorphous and hydrated manganese oxide (a-MnO2.nH(2)O) is the most promising for supercapacitor electrodes due to the low cost of the raw material. In the present work, amorphous manganese dioxide (a-MnO2.nH(2)O) is prepared by chemical co-precipitation of Mn(VII) and Mn(II) in water medium, giving small particles of relatively high surface area. Carbon nanotubes (CNTs) are proposed as an alternative additive of carbon black for improving the electrical conductivity of the manganese oxide electrodes used to build capacitors. The results demonstrate that CNTs are effective for increasing the capacitance and improving the electrochemical properties of the a-MnO2.nH(2)O electrodes which show a better capacitive behavior than with carbon black. This enhancement is due to the high entanglement of CNTs which form a network of open mesopores, allowing the bulk of MnO2 to be easily reached by the ions. The performance optimization requires a careful control of the electrolyte pH in order to avoid the irreversible reactions Mn(IV) to Mn(II) at the negative electrode and Mn(IV) to Mn(VII) at the positive one. (C) 2004 The Electrochemical Society.