Integrated study of first principles calculations and experimental measurements for Li-ionic conductivity in Al-doped solid-state LiGe2(PO4)3 electrolyte

Joonhee Kang, Habin Chung, Chilhoon Doh, Byoungwoo Kang, Byungchan Han

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

Understanding of the fundamental mechanisms causing significant enhancement of Li-ionic conductivity by Al3+ doping to a solid LiGe2(PO4)3 (LGP) electrolyte is pursued using first principles density functional theory (DFT) calculations combined with experimental measurements. Our results indicate that partial substitution Al3+ for Ge4+ in LiGe2(PO4)3 (LGP) with aliovalent (Li1+xAlxGe2-x(PO4)3, LAGP) improves the Li-ionic conductivity about four-orders of the magnitude. To unveil the atomic origin we calculate plausible diffusion paths of Li in LGP and LAGP materials using DFT calculations and a nudged elastic band method, and discover that LAGP had additional transport paths for Li with activation barriers as low as only 34% of the LGP. Notably, these new atomic channels manifest subtle electrostatic environments facilitating cooperative motions of at least two Li atoms. Ab-initio molecular dynamics predict Li-ionic conductivity for the LAGP system, which is amazingly agreed experimental measurement on in-house made samples. Consequently, we suggest that the excess amounts of Li caused by the aliovalent Al3+ doping to LGP lead to not only enhancing Li concentration but also opening new conducting paths with substantially decreases activation energies and thus high ionic conductivity of LAGP solid-state electrolyte.

Original languageEnglish
Pages (from-to)11-16
Number of pages6
JournalJournal of Power Sources
Volume293
DOIs
Publication statusPublished - 2015 Oct 20

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Ionic conductivity
ion currents
Electrolytes
electrolytes
solid state
Density functional theory
Doping (additives)
density functional theory
Molecular dynamics
Electrostatics
Substitution reactions
Activation energy
Chemical activation
activation
substitutes
electrostatics
molecular dynamics
activation energy
conduction
Atoms

All Science Journal Classification (ASJC) codes

  • Renewable Energy, Sustainability and the Environment
  • Energy Engineering and Power Technology
  • Physical and Theoretical Chemistry
  • Electrical and Electronic Engineering

Cite this

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title = "Integrated study of first principles calculations and experimental measurements for Li-ionic conductivity in Al-doped solid-state LiGe2(PO4)3 electrolyte",
abstract = "Understanding of the fundamental mechanisms causing significant enhancement of Li-ionic conductivity by Al3+ doping to a solid LiGe2(PO4)3 (LGP) electrolyte is pursued using first principles density functional theory (DFT) calculations combined with experimental measurements. Our results indicate that partial substitution Al3+ for Ge4+ in LiGe2(PO4)3 (LGP) with aliovalent (Li1+xAlxGe2-x(PO4)3, LAGP) improves the Li-ionic conductivity about four-orders of the magnitude. To unveil the atomic origin we calculate plausible diffusion paths of Li in LGP and LAGP materials using DFT calculations and a nudged elastic band method, and discover that LAGP had additional transport paths for Li with activation barriers as low as only 34{\%} of the LGP. Notably, these new atomic channels manifest subtle electrostatic environments facilitating cooperative motions of at least two Li atoms. Ab-initio molecular dynamics predict Li-ionic conductivity for the LAGP system, which is amazingly agreed experimental measurement on in-house made samples. Consequently, we suggest that the excess amounts of Li caused by the aliovalent Al3+ doping to LGP lead to not only enhancing Li concentration but also opening new conducting paths with substantially decreases activation energies and thus high ionic conductivity of LAGP solid-state electrolyte.",
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Integrated study of first principles calculations and experimental measurements for Li-ionic conductivity in Al-doped solid-state LiGe2(PO4)3 electrolyte. / Kang, Joonhee; Chung, Habin; Doh, Chilhoon; Kang, Byoungwoo; Han, Byungchan.

In: Journal of Power Sources, Vol. 293, 20.10.2015, p. 11-16.

Research output: Contribution to journalArticle

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AU - Han, Byungchan

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