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Blocking Directional Lithium Diffusion in Solid-State Electrolytes at the Interface: First-Principles Insights into the Impact of the Space Charge Layer
journal contribution
posted on 2023-02-20, 05:03 authored by G Dobhal, Tiffany WalshTiffany Walsh, Sherif AbbasSherif AbbasUnderstanding the degradation mechanisms in solid-state lithium-ion batteries at interfaces is fundamental for improving battery performance and for designing recycling methodologies for batteries. A key source of battery degradation is the presence of the space charge layer at the solid-state electrolyte-electrode interface and the impact that this layer has on the thermodynamics of the electrolyte structure. Currently, Li10GeP2S12in its pristine form has one of the highest lithium conductivities and has been used as a template for designing even higher conductivity derived structures. However, being an ionic material with mostly linear diffusion, it is prone to path-blocker defects, which we show here to be especially prevalent in the space charge layer. We analyze the thermodynamic properties of a number of path-blocker defects using density functional theory and their potential crystal decomposition and find that the presence of an electrostatic potential in the space charge layer elevates the likelihood of existence of these defects, which otherwise would not be likely to form in the bulk of the electrolyte away from electrodes. We use ab initio molecular dynamics to assess the impact of these defects on the diffusivity of the crystal and find that they all reduce the lithium diffusivity. While our work focuses on Li10GeP2S12, it is relevant to any solid-state electrolyte with mainly linear diffusion.
History
Journal
ACS Applied Materials and InterfacesVolume
14Pagination
55471-55479Location
United StatesPublisher DOI
ISSN
1944-8244eISSN
1944-8252Language
EnglishPublication classification
C1 Refereed article in a scholarly journalIssue
50Publisher
AMER CHEMICAL SOCUsage metrics
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No categories selectedKeywords
Science & TechnologyTechnologyNanoscience & NanotechnologyMaterials Science, MultidisciplinaryScience & Technology - Other TopicsMaterials Sciencelithium-ion batterydensity functional theoryspace charge layerab initio molecular dynamicssolid-state electrolyteCONDUCTOR LI10GEP2S12SUPERIONIC CONDUCTORSNATIVE DEFECTSCHALLENGESSTABILITYMODELSNSIChemical SciencesEngineering
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