Journal of the Electrochemical Society, Vol.147, No.3, 945-952, 2000
Synthesis and characterization of gamma-MnO2 samples with unusual structural parameters
gamma-MnO2 compounds are usually prepared by oxidative electrodeposition at high constant current density from boiling MnSO4 solutions. Their structure is made of an intergrowth of ramsdellite and pyrolusite blocks (with a percentage Pr (of rutile) of 40-50%) and of microtwinning (Mt) defects (with a percentage Mt > 40%). By varying the electrodeposition parameters, different materials have been obtained. Syntheses at constant voltage or current density lead to samples with 35% less than or equal to Pr less than or equal to 50% in which the Mn oxidation state can be modified by varying the electrodeposition temperature or the current density. Whatever the temperature, a pH increase of the bulk solution from 1.8 to 3.5 favors smaller Pr values. A decrease of the current density leads to more oxidized and better crystallized samples at 25 degrees C and smaller Mt values at 97 degrees C. New gamma-MnO2 with never-reported (Pr, Mt) combinations can be prepared by scanning the voltage (or the current) between selected values. Under such conditions Mt can be decreased by increasing the ratio between the total oxidation and reduction quantities of electricity. Upon annealing at 250 degrees C of samples with Pr < 50%, new compounds were obtained with unusually small Pr values and/or unusually large Mt values for heat-treated manganese dioxides.