The impact of oxygen vacancies on lithium vacancy formation and diffusion in Li2-xMnO3-δ

Christine James, Yan Wu, Brian W. Sheldon, Yue Qi

    Research output: Contribution to journalArticle

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    Abstract

    High-capacity battery cathode materials containing Li2MnO3 appear to be activated during the first electrochemical cycle through the generation of oxygen vacancies. These oxygen vacancies have been predicted to alter the atomistic scale structure of Li2MnO3 and thus impact the delithiation process. In order to understand the effects of these oxygen vacancies we computationally determine the location of lithium removal in Li2MnO3-δ (δ = 0, 0.0625 and 0.125) and study lithium diffusion in Li2-xMnO3-δ. This study shows that it is energetically favorable for the lithium vacancies to form in the neighboring positions of the oxygen vacancies, suggesting that there is a strong interaction between the two vacancy types. This interaction also inhibits the diffusion of the lithium-ions, as seen in ab-initio molecular dynamics simulations where less hopping of lithium atoms is observed when oxygen vacancies are present. Additionally, the oxygen vacancy containing structures lead to an increase in the energy barrier for lithium and the calculated diffusion coefficient decreases by ∼ 5 orders of magnitude from the perfect crystal structure.

    Original languageEnglish (US)
    Pages (from-to)87-94
    Number of pages8
    JournalSolid State Ionics
    Volume289
    DOIs
    StatePublished - Jun 1 2016

    Profile

    Oxygen vacancies
    Lithium
    Osteoradionecrosis
    lithium
    oxygen
    Feline Sarcoma Viruses
    Vacancies
    Ostertagiasis
    Energy barriers
    Molecular dynamics
    Cathodes
    Crystal structure
    Removal
    Atoms
    Computer simulation
    Ions
    Coumestrol
    African Swine Fever Virus
    Cytochrome c Group
    Nerve Crush

    ASJC Scopus subject areas

    • Materials Science(all)
    • Condensed Matter Physics
    • Chemistry(all)

    Cite this

    The impact of oxygen vacancies on lithium vacancy formation and diffusion in Li2-xMnO3-δ . / James, Christine; Wu, Yan; Sheldon, Brian W.; Qi, Yue.

    In: Solid State Ionics, Vol. 289, 01.06.2016, p. 87-94.

    Research output: Contribution to journalArticle

    James, Christine; Wu, Yan; Sheldon, Brian W.; Qi, Yue / The impact of oxygen vacancies on lithium vacancy formation and diffusion in Li2-xMnO3-δ .

    In: Solid State Ionics, Vol. 289, 01.06.2016, p. 87-94.

    Research output: Contribution to journalArticle

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    abstract = "High-capacity battery cathode materials containing Li2MnO3 appear to be activated during the first electrochemical cycle through the generation of oxygen vacancies. These oxygen vacancies have been predicted to alter the atomistic scale structure of Li2MnO3 and thus impact the delithiation process. In order to understand the effects of these oxygen vacancies we computationally determine the location of lithium removal in Li2MnO3-δ (δ = 0, 0.0625 and 0.125) and study lithium diffusion in Li2-xMnO3-δ. This study shows that it is energetically favorable for the lithium vacancies to form in the neighboring positions of the oxygen vacancies, suggesting that there is a strong interaction between the two vacancy types. This interaction also inhibits the diffusion of the lithium-ions, as seen in ab-initio molecular dynamics simulations where less hopping of lithium atoms is observed when oxygen vacancies are present. Additionally, the oxygen vacancy containing structures lead to an increase in the energy barrier for lithium and the calculated diffusion coefficient decreases by ∼ 5 orders of magnitude from the perfect crystal structure.",
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    AB - High-capacity battery cathode materials containing Li2MnO3 appear to be activated during the first electrochemical cycle through the generation of oxygen vacancies. These oxygen vacancies have been predicted to alter the atomistic scale structure of Li2MnO3 and thus impact the delithiation process. In order to understand the effects of these oxygen vacancies we computationally determine the location of lithium removal in Li2MnO3-δ (δ = 0, 0.0625 and 0.125) and study lithium diffusion in Li2-xMnO3-δ. This study shows that it is energetically favorable for the lithium vacancies to form in the neighboring positions of the oxygen vacancies, suggesting that there is a strong interaction between the two vacancy types. This interaction also inhibits the diffusion of the lithium-ions, as seen in ab-initio molecular dynamics simulations where less hopping of lithium atoms is observed when oxygen vacancies are present. Additionally, the oxygen vacancy containing structures lead to an increase in the energy barrier for lithium and the calculated diffusion coefficient decreases by ∼ 5 orders of magnitude from the perfect crystal structure.

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