Correlating Structural Disorder to Li+Ion Transport in Li4- xGe1- xSbxS4(0 ≤ x ≤ 0.2)

Bianca Helm; Nicolò Minafra; Björn Wankmiller; Matthias T. Agne; Cheng Li; Anatoliy Senyshyn; Michael Ryan Hansen; Wolfgang G. Zeier

doi:10.1021/acs.chemmater.2c00608

Correlating Structural Disorder to Li⁺Ion Transport in Li_{4- x}Ge_{1- x}Sb_xS₄(0 ≤ x ≤ 0.2)

Bianca Helm, Nicolò Minafra, Björn Wankmiller, Matthias T. Agne, Cheng Li, Anatoliy Senyshyn, Michael Ryan Hansen, Wolfgang G. Zeier

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Abstract

Strong compositional influences are known to affect the ionic transport within the thio-LISICON family; however, a deeper understanding of the resulting structure-transport correlations has up until now been lacking. Employing a combination of high-resolution neutron diffraction, impedance spectroscopy, and nuclear magnetic resonance spectroscopy, together with bond valence site energy calculations and the maximum entropy method for determining the underlying Li+ scattering density distribution of a crystal structure, this work assesses the impact of the Li+ substructure and charge carrier density on the ionic transport within the Li4-xGe1-xSbxS4 substitution series. By incorporating Sb5+ into Li4GeS4, an anisometric expansion of the unit cell is observed. An additional Li+ position is found as soon as (SbS4)3- polyhedra are present, leading to a better local polyhedral connectivity and a higher disorder in the Li+ substructure. Here, we are able to relate structural disorder to an increase in configurational entropy, together with a 2 order-of-magnitude increase in ionic conductivity. This result reinforces the typically believed paradigm that structural disorder leads to improvements in ionic transport.

Original language	English
Pages (from-to)	5558-5570
Number of pages	13
Journal	Chemistry of Materials
Volume	34
Issue number	12
DOIs	https://doi.org/10.1021/acs.chemmater.2c00608
State	Published - Jun 28 2022

Funding

The research was supported by the Federal Ministry of Education and Research (BMBF) within the project Festbatt under grant number 03XP0430F. B.W. is member of the International Graduate School for Battery Chemistry, Characterization, Analysis, Recycling and Application (BACCARA), which is funded by the Ministry for Culture and Science of North Rhine Westphalia, Germany. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.

Funders	Funder number
Ministry for Culture and Science of North Rhine Westphalia
Bundesministerium für Bildung und Forschung	03XP0430F

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10.1021/acs.chemmater.2c00608

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title = "Correlating Structural Disorder to Li+Ion Transport in Li4- xGe1- xSbxS4(0 ≤ x ≤ 0.2)",

abstract = "Strong compositional influences are known to affect the ionic transport within the thio-LISICON family; however, a deeper understanding of the resulting structure-transport correlations has up until now been lacking. Employing a combination of high-resolution neutron diffraction, impedance spectroscopy, and nuclear magnetic resonance spectroscopy, together with bond valence site energy calculations and the maximum entropy method for determining the underlying Li+ scattering density distribution of a crystal structure, this work assesses the impact of the Li+ substructure and charge carrier density on the ionic transport within the Li4-xGe1-xSbxS4 substitution series. By incorporating Sb5+ into Li4GeS4, an anisometric expansion of the unit cell is observed. An additional Li+ position is found as soon as (SbS4)3- polyhedra are present, leading to a better local polyhedral connectivity and a higher disorder in the Li+ substructure. Here, we are able to relate structural disorder to an increase in configurational entropy, together with a 2 order-of-magnitude increase in ionic conductivity. This result reinforces the typically believed paradigm that structural disorder leads to improvements in ionic transport.",

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AU - Agne, Matthias T.

AU - Li, Cheng

AU - Senyshyn, Anatoliy

AU - Hansen, Michael Ryan

AU - Zeier, Wolfgang G.

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N2 - Strong compositional influences are known to affect the ionic transport within the thio-LISICON family; however, a deeper understanding of the resulting structure-transport correlations has up until now been lacking. Employing a combination of high-resolution neutron diffraction, impedance spectroscopy, and nuclear magnetic resonance spectroscopy, together with bond valence site energy calculations and the maximum entropy method for determining the underlying Li+ scattering density distribution of a crystal structure, this work assesses the impact of the Li+ substructure and charge carrier density on the ionic transport within the Li4-xGe1-xSbxS4 substitution series. By incorporating Sb5+ into Li4GeS4, an anisometric expansion of the unit cell is observed. An additional Li+ position is found as soon as (SbS4)3- polyhedra are present, leading to a better local polyhedral connectivity and a higher disorder in the Li+ substructure. Here, we are able to relate structural disorder to an increase in configurational entropy, together with a 2 order-of-magnitude increase in ionic conductivity. This result reinforces the typically believed paradigm that structural disorder leads to improvements in ionic transport.

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Correlating Structural Disorder to Li⁺Ion Transport in Li_{4- x}Ge_{1- x}Sb_xS₄(0 ≤ x ≤ 0.2)

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