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First-principles calculations on structure and properties of amorphous Li5P4O8N3 (LiPON)

Sicolo, Sabrina and Albe, Karsten (2016):
First-principles calculations on structure and properties of amorphous Li5P4O8N3 (LiPON).
In: Journal of Power Sources, pp. 382-390, 331, ISSN 03787753,
[Online-Edition: http://dx.doi.org/10.1016/j.jpowsour.2016.09.059],
[Article]

Abstract

The structural, electronic and ion transport properties of an amorphous member of the LiPON family with non-trivial composition and cross-linking are studied by means of electronic structure calculations within Density Functional Theory. By a combination of an evolutionary algorithm followed by simulated annealing and alternatively by a rapid quenching protocol, structural models of disordered Li5P4O8N3 are generated, which are characterized by a local demixing in Li-rich and Li-poor layers. These structures have a composition close to what is found experimentally in thin films and contain all the expected diversely coordinated atoms, namely triply- and doubly-coordinated nitrogens and bridging and non-bridging oxygens. The issue of ionic conductivity is addressed by calculating defect formation energies and migration barriers of neutral and charged point defects. Li+ interstitials are energetically much preferred over vacancies, both when the lithium reservoir is metallic lithium and LiCoO2. The competitive formation of neutral Li interstitials when LiPON is contacted with metallic Li results in the chemical reduction of LiPON and the disruption of the network, as recently observed in experiments.

Item Type: Article
Erschienen: 2016
Creators: Sicolo, Sabrina and Albe, Karsten
Title: First-principles calculations on structure and properties of amorphous Li5P4O8N3 (LiPON)
Language: English
Abstract:

The structural, electronic and ion transport properties of an amorphous member of the LiPON family with non-trivial composition and cross-linking are studied by means of electronic structure calculations within Density Functional Theory. By a combination of an evolutionary algorithm followed by simulated annealing and alternatively by a rapid quenching protocol, structural models of disordered Li5P4O8N3 are generated, which are characterized by a local demixing in Li-rich and Li-poor layers. These structures have a composition close to what is found experimentally in thin films and contain all the expected diversely coordinated atoms, namely triply- and doubly-coordinated nitrogens and bridging and non-bridging oxygens. The issue of ionic conductivity is addressed by calculating defect formation energies and migration barriers of neutral and charged point defects. Li+ interstitials are energetically much preferred over vacancies, both when the lithium reservoir is metallic lithium and LiCoO2. The competitive formation of neutral Li interstitials when LiPON is contacted with metallic Li results in the chemical reduction of LiPON and the disruption of the network, as recently observed in experiments.

Journal or Publication Title: Journal of Power Sources
Volume: 331
Uncontrolled Keywords: DFT; Interfaces; Li-ion batteries; LiPON; Lithium phosphate glasses; Solid electrolytes
Divisions: 11 Department of Materials and Earth Sciences
11 Department of Materials and Earth Sciences > Material Science
11 Department of Materials and Earth Sciences > Material Science > Materials Modelling
Zentrale Einrichtungen
Zentrale Einrichtungen > University IT-Service and Computing Centre (HRZ)
Zentrale Einrichtungen > University IT-Service and Computing Centre (HRZ) > Hochleistungsrechner
Date Deposited: 29 Sep 2016 11:54
Official URL: http://dx.doi.org/10.1016/j.jpowsour.2016.09.059
Additional Information:

SFB 595

Identification Number: doi:10.1016/j.jpowsour.2016.09.059
Funders: This work has been financially supported by the DFG center of excellence 595, “Electrical Fatigue in Functional Materials” and DFG project AL-578/19-1. The authors gratefully acknowledge the computing time granted by the Lichtenberg, High Performance Computer of TU Darmstadt.
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