Electrostatic Spray Deposition-Based Manganese Oxide Films-From Pseudocapacitive Charge Storage Materials to Three-Dimensional Microelectrode Integrands.

In this study, porous manganese oxide (MnOx) thin films were synthesized via electrostatic spray deposition (ESD) and evaluated as pseudocapacitive electrode materials in neutral aqueous media. Very interestingly, the gravimetric specific capacitance of the ESD-based electrodes underwent a marked enhancement upon electrochemical cycling, from 72 F∙g(-1) to 225 F∙g(-1), with a concomitant improvement in kinetics and conductivity. The change in capacitance and resistivity is attributed to a partial electrochemical phase transformation from the spinel-type hausmannite Mn₃O₄ to the conducting layered birnessite MnO₂. Furthermore, the films were able to retain 88.4% of the maximal capacitance after 1000 cycles. Upon verifying the viability of the manganese oxide films for pseudocapacitive applications, the thin films were integrated onto carbon micro-pillars created via carbon microelectromechanical systems (C-MEMS) for examining their application as potential microelectrode candidates. In a symmetric two-electrode cell setup, the MnOx/C-MEMS microelectrodes were able to deliver specific capacitances as high as 0.055 F∙cm(-2) and stack capacitances as high as 7.4 F·cm(-3), with maximal stack energy and power densities of 0.51 mWh·cm(-3) and 28.3 mW·cm(-3), respectively. The excellent areal capacitance of the MnOx-MEs is attributed to the pseudocapacitive MnOx as well as the three-dimensional architectural framework provided by the carbon micro-pillars.