434657 Cation Incorporation Pseudocapacitance in a-MnO2

Wednesday, November 11, 2015: 1:45 PM
251C (Salt Palace Convention Center)
Matthias J. Young1, Aaron Holder2, Steven George2,3 and Charles B. Musgrave1, (1)Department of Chemical and Biological Engineering, University of Colorado, Boulder, CO, (2)Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, (3)Department of Mechanical Engineering, University of Colorado, Boulder, CO

Electrochemical supercapacitors utilizing α-MnO2 offer the possibility of both high power density and high energy density. Unfortunately, the mechanism of electrochemical charge storage in α-MnO2 and the effect of operating conditions on the charge storage mechanism are generally not well understood. Here, we present the first detailed charge storage mechanism of α-MnO2 and explain the capacity differences between α- and β-MnO2 using a combined theoretical electrochemical and band structure analysis. We identify the importance of the band gap, work function, the point of zero charge, and the tunnel sizes of the electrode material, as well as the pH and stability window of the electrolyte in determining the viability of a given electrode material. The high capacity of α-MnO2 results from cation induced charge-switching states in the band gap that overlap with the scanned potential allowed by the electrolyte. The charge-switching states originate from interstitial and substitutional cations (H+, Li+, Na+, and K+) incorporated into the material. Interstitial cations are found to induce charge-switching states by stabilizing Mn-O antibonding orbitals from the conduction band. Substitutional cations interact with O[2p] dangling bonds that are destabilized from the valence band by Mn vacancies to induce charge-switching states. We calculate the equilibrium electrochemical potentials at which these states are reduced and predict the effect of the electrochemical operating conditions on their contribution to charge storage. The mechanism and theoretical approach we report is general and can be used to computationally screen new materials for improved charge storage via ion incorporation.

Extended Abstract: File Not Uploaded
See more of this Session: Fundamentals of Electrochemical Processes II
See more of this Group/Topical: Engineering Sciences and Fundamentals