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research article

Mechanism of Charge Transport in Lithium Thiophosphate

Gigli, Lorenzo  
•
Tisi, Davide  
•
Grasselli, Federico  
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February 13, 2024
Chemistry of Materials

Lithium ortho-thiophosphate (Li3PS4) has emerged as a promising candidate for solid-state electrolyte batteries, thanks to its highly conductive phases, cheap components, and large electrochemical stability range. Nonetheless, the microscopic mechanisms of Li-ion transport in Li3PS4 are far from being fully understood, the role of PS4 dynamics in charge transport still being controversial. In this work, we build machine learning potentials targeting state-of-the-art DFT references (PBEsol, r2SCAN, and PBE0) to tackle this problem in all known phases of Li3PS4 (α, β, and γ), for large system sizes and time scales. We discuss the physical origin of the observed superionic behavior of Li3PS4: the activation of PS4 flipping drives a structural transition to a highly conductive phase, characterized by an increase in Li-site availability and by a drastic reduction in the activation energy of Li-ion diffusion. We also rule out any paddle-wheel effects of PS4 tetrahedra in the superionic phases─previously claimed to enhance Li-ion diffusion─due to the orders-of-magnitude difference between the rate of PS4 flips and Li-ion hops at all temperatures below melting. We finally elucidate the role of interionic dynamical correlations in charge transport, by highlighting the failure of the Nernst-Einstein approximation to estimate the electrical conductivity. Our results show a strong dependence on the target DFT reference, with PBE0 yielding the best quantitative agreement with experimental measurements not only for the electronic band gap but also for the electrical conductivity of β- and α-Li3PS4

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Type
research article
DOI
10.1021/acs.chemmater.3c02726
Scopus ID

2-s2.0-85184809566

Author(s)
Gigli, Lorenzo  

École Polytechnique Fédérale de Lausanne

Tisi, Davide  

École Polytechnique Fédérale de Lausanne

Grasselli, Federico  

École Polytechnique Fédérale de Lausanne

Ceriotti, Michele  

École Polytechnique Fédérale de Lausanne

Date Issued

2024-02-13

Published in
Chemistry of Materials
Volume

36

Issue

3

Start page

1482

End page

1496

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
COSMO  
FunderFunding(s)Grant NumberGrant URL

MARVEL National Centre of Competence in Research

Marie Skłodowska-Curie Action IF-EF-ST

101018557-TRANQUIL

Platform for Advanced Scientific Computing

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Available on Infoscience
January 16, 2025
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/242876
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