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Li4.3AlS3.3Cl0.7: A sulfide–chloride lithium ion conductor with highly disordered structure and increased conductivity

DOI: 10.1021/acs.chemmater.1c02751 DOI Help

Authors: Jacinthe Gamon (University of Liverpool) , Matthew S. Dyer (University of Liverpool) , Benjamin B. Duff (University of Liverpool) , Andrij Vasylenko (University of Liverpool) , Luke M. Daniels (University of Liverpool) , Marco Zanella (University of Liverpool) , Michael W. Gaultois (University of Liverpool) , Frédéric Blanc (University of Liverpool) , John B. Claridge (University of Liverpool) , Matthew J. Rosseinsky (University of Liverpool)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemistry Of Materials

State: Published (Approved)
Published: November 2021

Open Access Open Access

Abstract: Mixed anion materials and anion doping are very promising strategies to improve solid-state electrolyte properties by enabling an optimized balance between good electrochemical stability and high ionic conductivity. In this work, we present the discovery of a novel lithium aluminum sulfide–chloride phase, obtained by substitution of chloride for sulfur in Li3AlS3 and Li5AlS4 materials. The structure is strongly affected by the presence of chloride anions on the sulfur site, as the substitution was shown to be directly responsible for the stabilization of a higher symmetry phase presenting a large degree of cationic site disorder, as well as disordered octahedral lithium vacancies. The effect of disorder on the lithium conductivity properties was assessed by a combined experimental–theoretical approach. In particular, the conductivity is increased by a factor 103 compared to the pure sulfide phase. Although it remains moderate (10–6 S·cm–1), ab initio molecular dynamics and maximum entropy (applied to neutron diffraction data) methods show that disorder leads to a 3D diffusion pathway, where Li atoms move thanks to a concerted mechanism. An understanding of the structure–property relationships is developed to determine the limiting factor governing lithium ion conductivity. This analysis, added to the strong step forward obtained in the determination of the dimensionality of diffusion, paves the way for accessing even higher conductivity in materials comprising an hcp anion arrangement.

Journal Keywords: Chemical structure; Anions; Electrical conductivity; Layers; Lithium

Diamond Keywords: Batteries; Lithium-ion

Subject Areas: Chemistry, Materials, Energy

Instruments: I11-High Resolution Powder Diffraction

Added On: 15/11/2021 09:59


Discipline Tags:

Physical Chemistry Energy Energy Storage Materials Science Energy Materials Chemistry

Technical Tags:

Diffraction X-ray Powder Diffraction