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Title: The Unified Electrochemical Band Diagram Framework: Understanding the Driving Forces of Materials Electrochemistry

Recent work that establishes a picture of the driving forces that govern material transformations and degradation in electrochemical environments to enable the ab initio design of electrochemical materials is highlighted. Select prototype systems are used to describe how the interplay between materials properties such as crystal field splitting, band edge energies, surface termination, material length scale, dielectric constant, and isoelectric point, and electrolyte properties such as pH and ion type, impacts electrochemical behavior - i.e., redox potentials, reaction enthalpies, reactivity, and decoupled ionic/electronic processes. Ab initio modeling of charged defects and intercalants within the grand canonical unified electrochemical band-diagram (UEB) framework is shown to enable the quantitative prediction of electrochemical materials behavior. UEB combines electrochemical theory, charged defect theory, and band diagram descriptions and can be used both for materials discovery and development. First, a pedagogical description of the UEB framework is presented, and then the application of this framework to reveal mechanisms for high rate electronic charge storage in cation incorporated α.-MnO 2 and λ-MnO 2, high desalination efficiency of thin-film NaMn 4O 8, and the flat charge/discharge profile of FePO 4 is reviewed. Finally, new prospects for the application of the UEB framework to electrolyte design, interfacial engineering,more » and catalysis are suggested.« less
Authors:
 [1] ;  [2] ; ORCiD logo [2]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Univ. of Colorado, Boulder, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Report Number(s):
NREL/JA-5K00-72374
Journal ID: ISSN 1616-301X
Grant/Contract Number:
AC36-08GO28308; EE0008088
Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Name: Advanced Functional Materials; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Research Org:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; charge storage materials; defect theory; DFT calculations; electrochemical materials; interfacial engineering
OSTI Identifier:
1470972
Alternate Identifier(s):
OSTI ID: 1465894

Young, Matthias J., Holder, Aaron M., and Musgrave, Charles B.. The Unified Electrochemical Band Diagram Framework: Understanding the Driving Forces of Materials Electrochemistry. United States: N. p., Web. doi:10.1002/adfm.201803439.
Young, Matthias J., Holder, Aaron M., & Musgrave, Charles B.. The Unified Electrochemical Band Diagram Framework: Understanding the Driving Forces of Materials Electrochemistry. United States. doi:10.1002/adfm.201803439.
Young, Matthias J., Holder, Aaron M., and Musgrave, Charles B.. 2018. "The Unified Electrochemical Band Diagram Framework: Understanding the Driving Forces of Materials Electrochemistry". United States. doi:10.1002/adfm.201803439.
@article{osti_1470972,
title = {The Unified Electrochemical Band Diagram Framework: Understanding the Driving Forces of Materials Electrochemistry},
author = {Young, Matthias J. and Holder, Aaron M. and Musgrave, Charles B.},
abstractNote = {Recent work that establishes a picture of the driving forces that govern material transformations and degradation in electrochemical environments to enable the ab initio design of electrochemical materials is highlighted. Select prototype systems are used to describe how the interplay between materials properties such as crystal field splitting, band edge energies, surface termination, material length scale, dielectric constant, and isoelectric point, and electrolyte properties such as pH and ion type, impacts electrochemical behavior - i.e., redox potentials, reaction enthalpies, reactivity, and decoupled ionic/electronic processes. Ab initio modeling of charged defects and intercalants within the grand canonical unified electrochemical band-diagram (UEB) framework is shown to enable the quantitative prediction of electrochemical materials behavior. UEB combines electrochemical theory, charged defect theory, and band diagram descriptions and can be used both for materials discovery and development. First, a pedagogical description of the UEB framework is presented, and then the application of this framework to reveal mechanisms for high rate electronic charge storage in cation incorporated α.-MnO2 and λ-MnO2, high desalination efficiency of thin-film NaMn4O8, and the flat charge/discharge profile of FePO4 is reviewed. Finally, new prospects for the application of the UEB framework to electrolyte design, interfacial engineering, and catalysis are suggested.},
doi = {10.1002/adfm.201803439},
journal = {Advanced Functional Materials},
number = ,
volume = ,
place = {United States},
year = {2018},
month = {8}
}

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