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Analysis of Lithium Insertion/Desorption Reaction at Interfaces between Graphite Electrodes and Electrolyte Solution Using Density Functional + Implicit Solvation Theory

  • Jun Haruyama*
    Jun Haruyama
    Research Center for Computational Design of Advanced Functional Materials (CD-FMat), National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, Ibaraki 305-8568, Japan
    *E-mail: [email protected]
    More by Jun Haruyama
  • Tamio Ikeshoji
    Tamio Ikeshoji
    Research Center for Computational Design of Advanced Functional Materials (CD-FMat), National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, Ibaraki 305-8568, Japan
  • , and 
  • Minoru Otani*
    Minoru Otani
    Research Center for Computational Design of Advanced Functional Materials (CD-FMat), National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, Ibaraki 305-8568, Japan
    *E-mail: [email protected]
    More by Minoru Otani
Cite this: J. Phys. Chem. C 2018, 122, 18, 9804–9810
Publication Date (Web):April 18, 2018
https://doi.org/10.1021/acs.jpcc.8b01979
Copyright © 2018 American Chemical Society

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    Abstract

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    The charge transfer reaction at the electrode/solution interface is regarded as a major component that limits the current densities of Li-ion batteries. A combination of density functional theory for the electronic structure calculations of an electrode and a reacting component with implicit solvation theory for an electrolyte solution is used for the lithium insertion/desorption reaction (R). At the interfaces between tilted-graphite electrodes and a 1 M LiPF6 ethylene carbonate solution, the energy landscapes of reaction R are revealed under constant electron chemical potential conditions. Across the transition state where the Li forms a half solvation shell, the reacting Li inside the electrode changes to a full solvation structure in the solution accompanied by electron transfer. On graphite with two tilt angles, the activation energies at the equilibrium potentials of reaction R are approximately 0.6 eV, which is consistent with the electrochemical impedance spectroscopy measurements. However, opposite-sign charges are obtained on the two angle surfaces, which can be well explained by the work functions on the tilted graphite. This study paves the way for the quantitative analysis of the charge-transfer reactions in electrochemical devices under electrochemically defined environments.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.8b01979.

    • Bulk atomic structures and cell parameters of AB-stacked graphite, LiC12, and LiC6. Free energy differences and electromotive forces between discharged and charged states. Configurations of atomic structures, unit cells, model indices, and cell parameters of the LinC6mHl slabs for ESM-RISM simulations. Reference sites of EC and PF6. Effective charges and Lennard-Jones parameters. Numbers of excluded electrons and chemical potential of 90° and 30° tilted graphite. Double layer structures of the RISM solvents. Configuration of the Li reaction path of 30° graphite. Charge distributions of the RISM solvents. Profiles of grand potential of various stoichiometry models. Vacancy formation energies for LiC12 model slabs. Atomic structures of 0°, 30°, 60°, and 90° graphite slabs for the calculation of work functions (PDF)

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