Electroless preparation and ASAXS microstructural analysis of pseudocapacitive carbon manganese oxide supercapacitor electrodes.

Anomalous small angle X-ray scattering (ASAXS) has been utilized as a noninvasive, integral tool to access the structural properties of carbon xerogel-manganese oxide electrodes with nanometer resolution. As these electrodes constitute the elementary functional units in supercapacitors and as their microstructure governs the macroscopic electrical performance, it is essential to gain a detailed morphological understanding of the underlying carbon particle scaffold coated with manganese oxide. We demonstrate that, in this regard, ASAXS provides a powerful technique and in combination with a theoretical core-shell model enables a quantitative estimation of the relevant structural parameters. As a result, we determined the thicknesses of the solution deposited MnO2 shells to range between 3 and 26 nm depending on the carbon particle size and thus on their effective surface area. By our core-shell modeling we conclude the revealed manganese oxide coatings on the carbon support to be rather thick, but nevertheless to show a high uniformity in thickness. At 1.8 ± 0.2 to 2.2 ± 0.1 g/cm(3) the related effective MnO2 densities of the shells are about 30% lower than the corresponding bulk density of 3.0 g/cm(3). This mainly originates from a substructure within the shell, whose growth is controlled by a pronounced reduction of the manganese precursor during layer formation. Finally, the presented ASAXS data are complemented by SEM and N2 sorption measurements, proving not only qualitatively the proposed flake-like MnO2 surface morphology but also confirming quantitatively the manganese shell thickness, complementary, on a local scale.