Ab Initio Study of the Influence of Structural Defects on the Electrochemical Properties of MnO$_{\mathrm{2}}$ in Rechargeable Zn/MnO$_{\mathrm{2}}$ Alkaline Batteries

ORAL

Abstract

The performance of MnO$_{\mathrm{2}}$ electrodes in rechargeable solid-state alkaline Zn/MnO$_{\mathrm{2\thinspace }}$batteries can be enhanced by nanostructuring and by introducing cation and oxygen vacancies into the crystal structure of MnO$_{\mathrm{2}}$. However, the mechanism of this enhancement has not been investigated in detail. We apply \textit{ab initio} density functional computational methods to study the mechanism of hydrogen ion insertion into the structures of $\beta $-, R-, and $\gamma $-MnO$_{\mathrm{2}}$ polymorphs containing cation vacancies, oxygen vacancies, and surfaces. Our calculations show that the presence of bulk defects and surfaces significantly changes the binding energies of hydrogen ions inserted into the crystal structures of MnO$_{\mathrm{2}}$ polymorphs. The results of our study show that surfaces and structural defects have a strong influence on the electrochemical properties of MnO$_{\mathrm{2}}$.

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Authors

  • Nirajan Paudel

    Department of Physics, New Mexico State University, Las Cruces, New Mexico 88003, USA

  • Barry Ritchie

    University of New Mexico, Ion Linac Systems, Tech-X Corporation, Los Alamos National Laboratory, Ronald Reagan UCLA Medical Center, Brigham Young University, Brigham Young University - Provo, United States Air Force Academy, university of Michigan, SISSA, Trieste, Stanford University, Worcester Polytechnic Institute, Grinnell College, Department of Physics, Arizona State University, Brookhaven National Laboratory, University of Southern California, Argonne National Laboratory, Department of Electrical and Computer Engineering, University of New Mexico, Department of Electrical and Computer Engineering and Department of Mechanical Engineering, University of New Mexico, Lock Haven University, Illinois State University, Department of Physics, Utah State University, Logan, Utah, 84322, Department of Physics, New Mexico State University, Las Cruces, New Mexico 88003, USA, Department of Materials, Devices, and Energy Technologies, Sandia National Laboratories, Albuquerque, New Mexico 87185, USA, Kyoto University, University of Guadalajara, University of Florida, Embry-Riddle Aeronautical University, Air Force Research Laboratory, Space Vehicles Directorate, Assurance Technology Corporation, Carlisle, MA, Georgia Tech Research Institute, Atlanta, GA, Utah State University, Georgia Institute of Technology, University of Tennessee, Knoxville, Arizona State University, Department of Physics, United States Air Force Academy, 80840 USAFA, CO, USA, Shaffer Consulting Inc, Max Planck Institute for Astrophysics, Harvard University, Max Planck Institute for Gravitational Physics, Albert Einstein Institute, ASU

  • Barry Ritchie

    University of New Mexico, Ion Linac Systems, Tech-X Corporation, Los Alamos National Laboratory, Ronald Reagan UCLA Medical Center, Brigham Young University, Brigham Young University - Provo, United States Air Force Academy, university of Michigan, SISSA, Trieste, Stanford University, Worcester Polytechnic Institute, Grinnell College, Department of Physics, Arizona State University, Brookhaven National Laboratory, University of Southern California, Argonne National Laboratory, Department of Electrical and Computer Engineering, University of New Mexico, Department of Electrical and Computer Engineering and Department of Mechanical Engineering, University of New Mexico, Lock Haven University, Illinois State University, Department of Physics, Utah State University, Logan, Utah, 84322, Department of Physics, New Mexico State University, Las Cruces, New Mexico 88003, USA, Department of Materials, Devices, and Energy Technologies, Sandia National Laboratories, Albuquerque, New Mexico 87185, USA, Kyoto University, University of Guadalajara, University of Florida, Embry-Riddle Aeronautical University, Air Force Research Laboratory, Space Vehicles Directorate, Assurance Technology Corporation, Carlisle, MA, Georgia Tech Research Institute, Atlanta, GA, Utah State University, Georgia Institute of Technology, University of Tennessee, Knoxville, Arizona State University, Department of Physics, United States Air Force Academy, 80840 USAFA, CO, USA, Shaffer Consulting Inc, Max Planck Institute for Astrophysics, Harvard University, Max Planck Institute for Gravitational Physics, Albert Einstein Institute, ASU

  • Barry Ritchie

    University of New Mexico, Ion Linac Systems, Tech-X Corporation, Los Alamos National Laboratory, Ronald Reagan UCLA Medical Center, Brigham Young University, Brigham Young University - Provo, United States Air Force Academy, university of Michigan, SISSA, Trieste, Stanford University, Worcester Polytechnic Institute, Grinnell College, Department of Physics, Arizona State University, Brookhaven National Laboratory, University of Southern California, Argonne National Laboratory, Department of Electrical and Computer Engineering, University of New Mexico, Department of Electrical and Computer Engineering and Department of Mechanical Engineering, University of New Mexico, Lock Haven University, Illinois State University, Department of Physics, Utah State University, Logan, Utah, 84322, Department of Physics, New Mexico State University, Las Cruces, New Mexico 88003, USA, Department of Materials, Devices, and Energy Technologies, Sandia National Laboratories, Albuquerque, New Mexico 87185, USA, Kyoto University, University of Guadalajara, University of Florida, Embry-Riddle Aeronautical University, Air Force Research Laboratory, Space Vehicles Directorate, Assurance Technology Corporation, Carlisle, MA, Georgia Tech Research Institute, Atlanta, GA, Utah State University, Georgia Institute of Technology, University of Tennessee, Knoxville, Arizona State University, Department of Physics, United States Air Force Academy, 80840 USAFA, CO, USA, Shaffer Consulting Inc, Max Planck Institute for Astrophysics, Harvard University, Max Planck Institute for Gravitational Physics, Albert Einstein Institute, ASU