Self-Assembled Epitaxial Cathode–Electrolyte Nanocomposites for 3D Microbatteries

[Image: see text] The downscaling of electronic devices requires rechargeable microbatteries with enhanced energy and power densities. Here, we evaluate self-assembled vertically aligned nanocomposite (VAN) thin films as a platform to create high-performance three-dimensional (3D) microelectrodes. This study focuses on controlling the VAN formation to enable interface engineering between the LiMn(2)O(4) cathode and the (Li,La)TiO(3) solid electrolyte. Electrochemical analysis in a half cell against lithium metal showed the absence of sharp redox peaks due to the confinement in the electrode pillars at the nanoscale. The (100)-oriented VAN thin films showed better rate capability and stability during extensive cycling due to the better alignment to the Li-diffusion channels. However, an enhanced pseudocapacitive contribution was observed for the increased total surface area within the (110)-oriented VAN thin films. These results demonstrate for the first time the electrochemical behavior of cathode–electrolyte VANs for lithium-ion 3D microbatteries while pointing out the importance of control over the vertical interfaces.