In this study, nanometer thin graphitic carbon coatings were applied as an adhesion layer for the growth of submicron to micron thick electrolytic manganese dioxide (EMD) films for thin-film energy storage devices. The graphitic carbon coating served not only as current collector and adhesion layer between the EMD and the substrate, but also prevented the oxidation of the non-noble TiN substrate during the anodic deposition process. The EMD films consisted of a network of interconnected nanometer-size particles with around 50% porosity. The ability to grow a few hundred nanometer thick EMD film with good adhesion to the current collector is critical for reliable thin-film batteries on high aspect ratio microstructured surfaces. Thin EMD films grown on our graphitic carbon coated TiN substrates showed improved reversible Li-ion intercalation kinetics and increased cycle life compared to similar films deposited on noble metal platinum substrates, thus demonstrating the improved interface properties using the graphitic carbon buffer layer.

In this work, we present the electrochemical deposition of manganese dioxide (MnO2) thin films on carbon-coated TiN/Si micro-pillars. The carbon buffer layer, grown by plasma enhanced chemical vapor deposition (PECVD), is used as a protective coating for the underlying TiN current collector from oxidation, during the film deposition, while improving the electrical conductivity of the stack. A conformal electrolytic MnO2 (EMD) coating is successfully achieved on high aspect ratio C/TiN/Si pillar arrays by tailoring the deposition process. Lithiation/Delithiation cycling tests have been performed. Reversible insertion and extraction of Li+ through EMD structure are observed. The fabricated stack is thus considered as a good candidate not only for 3D micorbatteries but also for other energy storage applications.