Elucidating lithium-ion and proton dynamics in anti-perovskite solid electrolytes

James Dawson, Tavleen S. Attari, Hungru Chen, Steffen P. Emge, Karen E. Johnston, Muhammed Islam

Research output: Contribution to journalArticle

13 Citations (Scopus)
3 Downloads (Pure)

Abstract

All-solid-state Li-ion batteries are currently attracting considerable research attention as they present a viable opportunity for increased energy density and safety when compared to conventional liquid electrolyte-based devices. The Li-rich anti-perovskite Li3−xOHxCl has generated recent interest as a potential solid electrolyte material, but its lithium and proton transport capabilities as a function of composition are not fully characterised. In this work, we apply a combination of ab initio molecular dynamics and 1H, 2H and 7Li solid-state NMR spectroscopy to study the mobility of lithium ions and protons in Li3−xOHxCl. Our calculations predict a strongly exothermic hydration enthalpy for Li3OCl, which explains the ease with which this material absorbs moisture and the difficulty in synthesising moisture-free samples. We show that the activation energy for Li-ion conduction increases with increasing proton content. The atomistic simulations indicate fast Li-ion diffusion but rule out the contribution of long-range proton diffusion. These findings are supported by variable-temperature solid-state NMR experiments, which indicate localised proton motion and long-range Li-ion mobility that are intimately connected. Our findings confirm that Li3−xOHxCl is a promising solid electrolyte material for all-solid-state Li-ion batteries.
Original languageEnglish
Pages (from-to)2993-3002
Number of pages10
JournalEnergy & Environmental Science
Volume11
Issue number10
Early online date30 Jul 2018
DOIs
Publication statusPublished - 1 Oct 2018

Fingerprint

Solid electrolytes
perovskite
lithium
Lithium
Perovskite
electrolyte
Protons
Ions
ion
Moisture
nuclear magnetic resonance
moisture
Hydration
Electrolytes
Nuclear magnetic resonance spectroscopy
Molecular dynamics
Enthalpy
enthalpy
hydration
activation energy

ASJC Scopus subject areas

  • Environmental Chemistry
  • Renewable Energy, Sustainability and the Environment
  • Nuclear Energy and Engineering
  • Pollution

Cite this

Elucidating lithium-ion and proton dynamics in anti-perovskite solid electrolytes. / Dawson, James; Attari, Tavleen S.; Chen, Hungru; Emge, Steffen P.; Johnston, Karen E.; Islam, Muhammed.

In: Energy & Environmental Science, Vol. 11, No. 10, 01.10.2018, p. 2993-3002.

Research output: Contribution to journalArticle

Dawson, James ; Attari, Tavleen S. ; Chen, Hungru ; Emge, Steffen P. ; Johnston, Karen E. ; Islam, Muhammed. / Elucidating lithium-ion and proton dynamics in anti-perovskite solid electrolytes. In: Energy & Environmental Science. 2018 ; Vol. 11, No. 10. pp. 2993-3002.
@article{e657da352e854de9b69a6c8762ec34c7,
title = "Elucidating lithium-ion and proton dynamics in anti-perovskite solid electrolytes",
abstract = "All-solid-state Li-ion batteries are currently attracting considerable research attention as they present a viable opportunity for increased energy density and safety when compared to conventional liquid electrolyte-based devices. The Li-rich anti-perovskite Li3−xOHxCl has generated recent interest as a potential solid electrolyte material, but its lithium and proton transport capabilities as a function of composition are not fully characterised. In this work, we apply a combination of ab initio molecular dynamics and 1H, 2H and 7Li solid-state NMR spectroscopy to study the mobility of lithium ions and protons in Li3−xOHxCl. Our calculations predict a strongly exothermic hydration enthalpy for Li3OCl, which explains the ease with which this material absorbs moisture and the difficulty in synthesising moisture-free samples. We show that the activation energy for Li-ion conduction increases with increasing proton content. The atomistic simulations indicate fast Li-ion diffusion but rule out the contribution of long-range proton diffusion. These findings are supported by variable-temperature solid-state NMR experiments, which indicate localised proton motion and long-range Li-ion mobility that are intimately connected. Our findings confirm that Li3−xOHxCl is a promising solid electrolyte material for all-solid-state Li-ion batteries.",
author = "James Dawson and Attari, {Tavleen S.} and Hungru Chen and Emge, {Steffen P.} and Johnston, {Karen E.} and Muhammed Islam",
year = "2018",
month = "10",
day = "1",
doi = "10.1039/C8EE00779A",
language = "English",
volume = "11",
pages = "2993--3002",
journal = "Energy & Environmental Science",
issn = "1754-5692",
publisher = "Royal Society of Chemistry",
number = "10",

}

TY - JOUR

T1 - Elucidating lithium-ion and proton dynamics in anti-perovskite solid electrolytes

AU - Dawson, James

AU - Attari, Tavleen S.

AU - Chen, Hungru

AU - Emge, Steffen P.

AU - Johnston, Karen E.

AU - Islam, Muhammed

PY - 2018/10/1

Y1 - 2018/10/1

N2 - All-solid-state Li-ion batteries are currently attracting considerable research attention as they present a viable opportunity for increased energy density and safety when compared to conventional liquid electrolyte-based devices. The Li-rich anti-perovskite Li3−xOHxCl has generated recent interest as a potential solid electrolyte material, but its lithium and proton transport capabilities as a function of composition are not fully characterised. In this work, we apply a combination of ab initio molecular dynamics and 1H, 2H and 7Li solid-state NMR spectroscopy to study the mobility of lithium ions and protons in Li3−xOHxCl. Our calculations predict a strongly exothermic hydration enthalpy for Li3OCl, which explains the ease with which this material absorbs moisture and the difficulty in synthesising moisture-free samples. We show that the activation energy for Li-ion conduction increases with increasing proton content. The atomistic simulations indicate fast Li-ion diffusion but rule out the contribution of long-range proton diffusion. These findings are supported by variable-temperature solid-state NMR experiments, which indicate localised proton motion and long-range Li-ion mobility that are intimately connected. Our findings confirm that Li3−xOHxCl is a promising solid electrolyte material for all-solid-state Li-ion batteries.

AB - All-solid-state Li-ion batteries are currently attracting considerable research attention as they present a viable opportunity for increased energy density and safety when compared to conventional liquid electrolyte-based devices. The Li-rich anti-perovskite Li3−xOHxCl has generated recent interest as a potential solid electrolyte material, but its lithium and proton transport capabilities as a function of composition are not fully characterised. In this work, we apply a combination of ab initio molecular dynamics and 1H, 2H and 7Li solid-state NMR spectroscopy to study the mobility of lithium ions and protons in Li3−xOHxCl. Our calculations predict a strongly exothermic hydration enthalpy for Li3OCl, which explains the ease with which this material absorbs moisture and the difficulty in synthesising moisture-free samples. We show that the activation energy for Li-ion conduction increases with increasing proton content. The atomistic simulations indicate fast Li-ion diffusion but rule out the contribution of long-range proton diffusion. These findings are supported by variable-temperature solid-state NMR experiments, which indicate localised proton motion and long-range Li-ion mobility that are intimately connected. Our findings confirm that Li3−xOHxCl is a promising solid electrolyte material for all-solid-state Li-ion batteries.

UR - http://www.scopus.com/inward/record.url?scp=85054999789&partnerID=8YFLogxK

U2 - 10.1039/C8EE00779A

DO - 10.1039/C8EE00779A

M3 - Article

VL - 11

SP - 2993

EP - 3002

JO - Energy & Environmental Science

JF - Energy & Environmental Science

SN - 1754-5692

IS - 10

ER -