High-Entropy Polyanionic Lithium Superionic Conductors

Florian Strauss; Jing Lin; Marie Duffiet; Kai Wang; Tatiana Zinkevich; Anna Lena Hansen; Sylvio Indris; Torsten Brezesinski

doi:10.1021/acsmaterialslett.1c00817

High-Entropy Polyanionic Lithium Superionic Conductors

Florian Strauss
, Jing Lin
, Marie Duffiet
, Kai Wang
, Tatiana Zinkevich
, Anna Lena Hansen
, Sylvio Indris
, Torsten Brezesinski

Powder Diffraction

Research output: Contribution to journal › Article › peer-review

64 Scopus citations

Abstract

High-entropy ceramics are attracting large interest because of their unique materials properties. Nevertheless, the effect of entropy on the lithium transport remains largely elusive. Here, we report, for the first time, about medium- and high-entropy polyanionic lithium superionic conductors crystallizing in the F-43m space group and adopting the so-called argyrodite structure. The Li6PS5[Cl0.33Br0.33I0.33], Li6P[S2.5Se2.5][Cl0.33Br0.33I0.33], and Li6.5[Ge0.5P0.5][S2.5Se2.5][Cl0.33Br0.33I0.33] materials were structurally characterized using complementary synchrotron and neutron scattering techniques in combination with 31P magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. We show that, in contrast to other high-entropy ceramics, an unequal distribution of elements over the respective crystallographic sites occurs in these materials. Using electrochemical impedance spectroscopy (EIS) and 7Li pulsed field gradient (PFG) NMR spectroscopy, we demonstrate that introducing entropy (compositional disorder) marginally affects the room-temperature ionic conductivity (∼10-3 S cm-1) but instead lowers the activation energy for conduction to 0.22 eV. Our results emphasize the possibility of increasing entropy in polyanionic materials, thereby opening up compositional space for the search of Li-ion conductors with unprecedented properties.

Original language	English
Pages (from-to)	418-423
Number of pages	6
Journal	ACS Materials Letters
Volume	4
Issue number	2
DOIs	https://doi.org/10.1021/acsmaterialslett.1c00817
State	Published - Feb 7 2022

Funding

F.S. is grateful to the Fonds der Chemischen Industrie for financial support through a Liebig fellowship. J.L. acknowledges the FCI for Ph.D. funding. This work was partially supported by BASF SE. This research used resources at the Spallation Neutron Source (SNS), a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory (ORNL). We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III, and we would like to thank Volodymyr Baran for assistance in using beamline P02.1.

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10.1021/acsmaterialslett.1c00817

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title = "High-Entropy Polyanionic Lithium Superionic Conductors",

abstract = "High-entropy ceramics are attracting large interest because of their unique materials properties. Nevertheless, the effect of entropy on the lithium transport remains largely elusive. Here, we report, for the first time, about medium- and high-entropy polyanionic lithium superionic conductors crystallizing in the F-43m space group and adopting the so-called argyrodite structure. The Li6PS5[Cl0.33Br0.33I0.33], Li6P[S2.5Se2.5][Cl0.33Br0.33I0.33], and Li6.5[Ge0.5P0.5][S2.5Se2.5][Cl0.33Br0.33I0.33] materials were structurally characterized using complementary synchrotron and neutron scattering techniques in combination with 31P magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. We show that, in contrast to other high-entropy ceramics, an unequal distribution of elements over the respective crystallographic sites occurs in these materials. Using electrochemical impedance spectroscopy (EIS) and 7Li pulsed field gradient (PFG) NMR spectroscopy, we demonstrate that introducing entropy (compositional disorder) marginally affects the room-temperature ionic conductivity (∼10-3 S cm-1) but instead lowers the activation energy for conduction to 0.22 eV. Our results emphasize the possibility of increasing entropy in polyanionic materials, thereby opening up compositional space for the search of Li-ion conductors with unprecedented properties.",

author = "Florian Strauss and Jing Lin and Marie Duffiet and Kai Wang and Tatiana Zinkevich and Hansen, \{Anna Lena\} and Sylvio Indris and Torsten Brezesinski",

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AU - Strauss, Florian

AU - Lin, Jing

AU - Duffiet, Marie

AU - Wang, Kai

AU - Zinkevich, Tatiana

AU - Hansen, Anna Lena

AU - Indris, Sylvio

AU - Brezesinski, Torsten

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N2 - High-entropy ceramics are attracting large interest because of their unique materials properties. Nevertheless, the effect of entropy on the lithium transport remains largely elusive. Here, we report, for the first time, about medium- and high-entropy polyanionic lithium superionic conductors crystallizing in the F-43m space group and adopting the so-called argyrodite structure. The Li6PS5[Cl0.33Br0.33I0.33], Li6P[S2.5Se2.5][Cl0.33Br0.33I0.33], and Li6.5[Ge0.5P0.5][S2.5Se2.5][Cl0.33Br0.33I0.33] materials were structurally characterized using complementary synchrotron and neutron scattering techniques in combination with 31P magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. We show that, in contrast to other high-entropy ceramics, an unequal distribution of elements over the respective crystallographic sites occurs in these materials. Using electrochemical impedance spectroscopy (EIS) and 7Li pulsed field gradient (PFG) NMR spectroscopy, we demonstrate that introducing entropy (compositional disorder) marginally affects the room-temperature ionic conductivity (∼10-3 S cm-1) but instead lowers the activation energy for conduction to 0.22 eV. Our results emphasize the possibility of increasing entropy in polyanionic materials, thereby opening up compositional space for the search of Li-ion conductors with unprecedented properties.

AB - High-entropy ceramics are attracting large interest because of their unique materials properties. Nevertheless, the effect of entropy on the lithium transport remains largely elusive. Here, we report, for the first time, about medium- and high-entropy polyanionic lithium superionic conductors crystallizing in the F-43m space group and adopting the so-called argyrodite structure. The Li6PS5[Cl0.33Br0.33I0.33], Li6P[S2.5Se2.5][Cl0.33Br0.33I0.33], and Li6.5[Ge0.5P0.5][S2.5Se2.5][Cl0.33Br0.33I0.33] materials were structurally characterized using complementary synchrotron and neutron scattering techniques in combination with 31P magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. We show that, in contrast to other high-entropy ceramics, an unequal distribution of elements over the respective crystallographic sites occurs in these materials. Using electrochemical impedance spectroscopy (EIS) and 7Li pulsed field gradient (PFG) NMR spectroscopy, we demonstrate that introducing entropy (compositional disorder) marginally affects the room-temperature ionic conductivity (∼10-3 S cm-1) but instead lowers the activation energy for conduction to 0.22 eV. Our results emphasize the possibility of increasing entropy in polyanionic materials, thereby opening up compositional space for the search of Li-ion conductors with unprecedented properties.

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High-Entropy Polyanionic Lithium Superionic Conductors

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