Lithium-ion Mobility in Li6B18(Li3N) and Li Vacancy Tuning in the Solid Solution Li6B18(Li3N)1−x(Li2O)x

Tassilo M.F. Restle; Lavinia Scherf; Jasmin V. Dums; Alexander G. Mutschke; Robert J. Spranger; Holger Kirchhain; Antti J. Karttunen; Leo van Wüllen; Thomas F. Fässler

doi:10.1002/anie.202213962

Lithium-ion Mobility in Li₆B₁₈(Li₃N) and Li Vacancy Tuning in the Solid Solution Li₆B₁₈(Li₃N)_1−x(Li₂O)_x

Tassilo M.F. Restle
, Lavinia Scherf
, Jasmin V. Dums
, Alexander G. Mutschke
, Robert J. Spranger
, Holger Kirchhain
, Antti J. Karttunen
, Leo van Wüllen
, Thomas F. Fässler^*

^*Corresponding author for this work

Technical University of Munich
TUMInt.Energy Research GmbH
University of Augsburg

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

9 Citations (Scopus)

64 Downloads (Pure)

Abstract

All-solid-state batteries are promising candidates for safe energy-storage systems due to non-flammable solid electrolytes and the possibility to use metallic lithium as an anode. Thus, there is a challenge to design new solid electrolytes and to understand the principles of ion conduction on an atomic scale. We report on a new concept for compounds with high lithium ion mobility based on a rigid open-framework boron structure. The host–guest structure Li₆B₁₈(Li₃N) comprises large hexagonal pores filled with (Formula presented.) Li₇N] strands that represent a perfect cutout from the structure of α-Li₃N. Variable-temperature ⁷Li NMR spectroscopy reveals a very high Li mobility in the template phase with a remarkably low activation energy below 19 kJ mol⁻¹ and thus much lower than pristine Li₃N. The formation of the solid solution of Li₆B₁₈(Li₃N) and Li₆B₁₈(Li₂O) over the complete compositional range allows the tuning of lithium defects in the template structure that is not possible for pristine Li₃N and Li₂O.

Original language	English
Article number	e202213962
Number of pages	9
Journal	Angewandte Chemie - International Edition
Volume	62
Issue number	10
DOIs	https://doi.org/10.1002/anie.202213962
Publication status	Published - 1 Mar 2023
MoE publication type	A1 Journal article-refereed

Funding

The authors are grateful to the Bavarian Ministry of Economic Affairs, Regional Development, and Energy for funding their research in the project “Industrialisierbarkeit von Festkörperelektrolytzellen”. A.J.K. thanks CSC—the Finnish IT Center for Science for computational resources. Open Access funding enabled and organized by Projekt DEAL. The authors are grateful to the Bavarian Ministry of Economic Affairs, Regional Development, and Energy for funding their research in the project “Industrialisierbarkeit von Festkörperelektrolytzellen”. A.J.K. thanks CSC—the Finnish IT Center for Science for computational resources. Open Access funding enabled and organized by Projekt DEAL.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

Keywords

Boride
Host Guest System
Ion Conduction
Lithim
Nitride

Access to Document

10.1002/anie.202213962Licence: CC BY

CHEM_Restle_et_al_Lithium‐ion_Mobility_2023_Angewandte_Chemie_Int_EdFinal published version, 3.1 MBLicence: CC BY

Cite this

@article{e667e803caa5483bb59cd8d6bf87efc4,

title = "Lithium-ion Mobility in Li6B18(Li3N) and Li Vacancy Tuning in the Solid Solution Li6B18(Li3N)1−x(Li2O)x",

abstract = "All-solid-state batteries are promising candidates for safe energy-storage systems due to non-flammable solid electrolytes and the possibility to use metallic lithium as an anode. Thus, there is a challenge to design new solid electrolytes and to understand the principles of ion conduction on an atomic scale. We report on a new concept for compounds with high lithium ion mobility based on a rigid open-framework boron structure. The host–guest structure Li6B18(Li3N) comprises large hexagonal pores filled with (Formula presented.) Li7N] strands that represent a perfect cutout from the structure of α-Li3N. Variable-temperature 7Li NMR spectroscopy reveals a very high Li mobility in the template phase with a remarkably low activation energy below 19 kJ mol−1 and thus much lower than pristine Li3N. The formation of the solid solution of Li6B18(Li3N) and Li6B18(Li2O) over the complete compositional range allows the tuning of lithium defects in the template structure that is not possible for pristine Li3N and Li2O.",

keywords = "Boride, Host Guest System, Ion Conduction, Lithim, Nitride",

author = "Restle, \{Tassilo M.F.\} and Lavinia Scherf and Dums, \{Jasmin V.\} and Mutschke, \{Alexander G.\} and Spranger, \{Robert J.\} and Holger Kirchhain and Karttunen, \{Antti J.\} and \{van W{\"u}llen\}, Leo and F{\"a}ssler, \{Thomas F.\}",

note = "Funding Information: The authors are grateful to the Bavarian Ministry of Economic Affairs, Regional Development, and Energy for funding their research in the project “Industrialisierbarkeit von Festk{\"o}rperelektrolytzellen”. A.J.K. thanks CSC—the Finnish IT Center for Science for computational resources. Open Access funding enabled and organized by Projekt DEAL. Publisher Copyright: {\textcopyright} 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

year = "2023",

month = mar,

day = "1",

doi = "10.1002/anie.202213962",

language = "English",

volume = "62",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

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number = "10",

}

TY - JOUR

T1 - Lithium-ion Mobility in Li6B18(Li3N) and Li Vacancy Tuning in the Solid Solution Li6B18(Li3N)1−x(Li2O)x

AU - Restle, Tassilo M.F.

AU - Scherf, Lavinia

AU - Dums, Jasmin V.

AU - Mutschke, Alexander G.

AU - Spranger, Robert J.

AU - Kirchhain, Holger

AU - Karttunen, Antti J.

AU - van Wüllen, Leo

AU - Fässler, Thomas F.

N1 - Funding Information: The authors are grateful to the Bavarian Ministry of Economic Affairs, Regional Development, and Energy for funding their research in the project “Industrialisierbarkeit von Festkörperelektrolytzellen”. A.J.K. thanks CSC—the Finnish IT Center for Science for computational resources. Open Access funding enabled and organized by Projekt DEAL. Publisher Copyright: © 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

PY - 2023/3/1

Y1 - 2023/3/1

N2 - All-solid-state batteries are promising candidates for safe energy-storage systems due to non-flammable solid electrolytes and the possibility to use metallic lithium as an anode. Thus, there is a challenge to design new solid electrolytes and to understand the principles of ion conduction on an atomic scale. We report on a new concept for compounds with high lithium ion mobility based on a rigid open-framework boron structure. The host–guest structure Li6B18(Li3N) comprises large hexagonal pores filled with (Formula presented.) Li7N] strands that represent a perfect cutout from the structure of α-Li3N. Variable-temperature 7Li NMR spectroscopy reveals a very high Li mobility in the template phase with a remarkably low activation energy below 19 kJ mol−1 and thus much lower than pristine Li3N. The formation of the solid solution of Li6B18(Li3N) and Li6B18(Li2O) over the complete compositional range allows the tuning of lithium defects in the template structure that is not possible for pristine Li3N and Li2O.

AB - All-solid-state batteries are promising candidates for safe energy-storage systems due to non-flammable solid electrolytes and the possibility to use metallic lithium as an anode. Thus, there is a challenge to design new solid electrolytes and to understand the principles of ion conduction on an atomic scale. We report on a new concept for compounds with high lithium ion mobility based on a rigid open-framework boron structure. The host–guest structure Li6B18(Li3N) comprises large hexagonal pores filled with (Formula presented.) Li7N] strands that represent a perfect cutout from the structure of α-Li3N. Variable-temperature 7Li NMR spectroscopy reveals a very high Li mobility in the template phase with a remarkably low activation energy below 19 kJ mol−1 and thus much lower than pristine Li3N. The formation of the solid solution of Li6B18(Li3N) and Li6B18(Li2O) over the complete compositional range allows the tuning of lithium defects in the template structure that is not possible for pristine Li3N and Li2O.

KW - Boride

KW - Host Guest System

KW - Ion Conduction

KW - Lithim

KW - Nitride

UR - https://www.scopus.com/pages/publications/85146389460

U2 - 10.1002/anie.202213962

DO - 10.1002/anie.202213962

M3 - Article

C2 - 36588091

AN - SCOPUS:85146389460

SN - 1433-7851

VL - 62

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 10

M1 - e202213962

ER -

Lithium-ion Mobility in Li₆B₁₈(Li₃N) and Li Vacancy Tuning in the Solid Solution Li₆B₁₈(Li₃N)_1−x(Li₂O)_x

Abstract

Funding

UN SDGs

Keywords

Access to Document

Other files and links

Fingerprint

CCDC 2207446: Experimental Crystal Structure Determination

CCDC 2207443: Experimental Crystal Structure Determination

CCDC 2207445: Experimental Crystal Structure Determination

Technical University Munich (TU Munich) Reports Findings in Science [Lithium-ion Mobility in Li6 B18 (Li3 N) and Li Vacancy Tuning in the Solid Solution Li6 B18 (Li3 N)1-x (Li2 O)x]

Cite this

Lithium-ion Mobility in Li6B18(Li3N) and Li Vacancy Tuning in the Solid Solution Li6B18(Li3N)1−x(Li2O)x

Abstract

Funding

UN SDGs

Keywords

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 2207446: Experimental Crystal Structure Determination

CCDC 2207443: Experimental Crystal Structure Determination

CCDC 2207445: Experimental Crystal Structure Determination

Press/Media

Technical University Munich (TU Munich) Reports Findings in Science [Lithium-ion Mobility in Li6 B18 (Li3 N) and Li Vacancy Tuning in the Solid Solution Li6 B18 (Li3 N)1-x (Li2 O)x]

Cite this

Lithium-ion Mobility in Li₆B₁₈(Li₃N) and Li Vacancy Tuning in the Solid Solution Li₆B₁₈(Li₃N)_1−x(Li₂O)_x