Acta Materialia, volume 175, pages 426-435

Exploring Li-ion conductivity in cubic, tetragonal and mixed-phase Al-substituted Li7La3Zr2O12 using atomistic simulations and effective medium theory

Mauricio Hernandez Bonilla ¹

Fabián A. García Daza ¹

Javier Carrasco ²

Elena V. Akhmatskaya ^{1, 3}

Hide authors affiliations Show authors affiliations: 3 affiliations

BCAM - Basque Center for Applied Mathematics, Alameda de Mazarredo 14, E-480C09, Bilbao, Spain |

CIC EnergiGUNE, Albert Einstein 48, E-01510, Miñano, Spain |

IKERBASQUE, Basque Foundation for Science, María Díaz de Haro 3, E-48013, Bilbao, Spain |

Publication type: Journal Article

Publication date: 2019-08-01

Elsevier

Journal: Acta Materialia

Quartile SCImago

Quartile WOS

Impact factor: 9.4

ISSN: 13596454

DOI: 10.1016/j.actamat.2019.06.033

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Metals and Alloys

Ceramics and Composites

Electronic, Optical and Magnetic Materials

Polymers and Plastics

Abstract

Garnet Li 7 La 3 Zr 2 O 12 (LLZO) is a promising solid electrolyte candidate for solid-state Li-ion batteries, but at room temperature it crystallizes in a poorly Li-ion conductive tetragonal phase. To this end, partial substitution of Li + by Al 3+ ions is an effective way to stabilize the highly conductive cubic phase at room temperature. Yet, fundamental aspects regarding this aliovalent substitution remain poorly understood. In this work, we use molecular dynamics and advanced hybrid Monte Carlo methods for systematic study of the room temperature Li-ion diffusion in tetragonal and cubic LLZO to shed light on important open questions. We find that Al substitution in tetrahedral sites of the tetragonal LLZO allows previously inaccessible sites to become available, which enhances Li-ion conductivity. In contrast, in the cubic phase Li-ion diffusion paths become blocked in the vicinity of Al ions, resulting in a decrease of Li-ion conductivity. Moreover, combining the conductivities of individual phases through an effective medium approximation allowed us to estimate the conductivities of cubic/tetragonal phase mixtures that are in good agreement with those reported in several experimental works. This suggests that phase coexistence (due to phase equilibrium or gradients in Al content within a sample) could have a significant impact on the conductivity of Al-substituted LLZO, particularly at low contents of Al 3+ . Overall, by making a thorough comparison with reported experimental data, the theoretical study and simulations of this work advance our current understanding of Li-ion mobility in Al-substituted LLZO garnets and might guide future in-depth characterization experiments of this relevant energy storage material.

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Small	Small, 1, 5.56% Small 1 publication, 5.56%
ACS applied materials & interfaces	ACS applied materials & interfaces, 1, 5.56% ACS applied materials & interfaces 1 publication, 5.56%
ACS Applied Energy Materials	ACS Applied Energy Materials, 1, 5.56% ACS Applied Energy Materials 1 publication, 5.56%
Macromolecules	Macromolecules, 1, 5.56% Macromolecules 1 publication, 5.56%
SEMA SIMAI Springer Series	SEMA SIMAI Springer Series, 1, 5.56% SEMA SIMAI Springer Series 1 publication, 5.56%
Annual Review of Materials Research	Annual Review of Materials Research, 1, 5.56% Annual Review of Materials Research 1 publication, 5.56%
International Journal of Molecular Sciences	International Journal of Molecular Sciences, 1, 5.56% International Journal of Molecular Sciences 1 publication, 5.56%
Chemistry of Materials	Chemistry of Materials, 1, 5.56% Chemistry of Materials 1 publication, 5.56%
Journal of Materials Chemistry A	Journal of Materials Chemistry A, 1, 5.56% Journal of Materials Chemistry A 1 publication, 5.56%
Frontiers in Energy Research	Frontiers in Energy Research, 1, 5.56% Frontiers in Energy Research 1 publication, 5.56%
Journal of Energy Chemistry	Journal of Energy Chemistry, 1, 5.56% Journal of Energy Chemistry 1 publication, 5.56%
Russian Chemical Reviews	Russian Chemical Reviews, 1, 5.56% Russian Chemical Reviews 1 publication, 5.56%
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Elsevier	Elsevier, 5, 27.78% Elsevier 5 publications, 27.78%
American Chemical Society (ACS)	American Chemical Society (ACS), 4, 22.22% American Chemical Society (ACS) 4 publications, 22.22%
The Electrochemical Society	The Electrochemical Society, 1, 5.56% The Electrochemical Society 1 publication, 5.56%
IOP Publishing	IOP Publishing, 1, 5.56% IOP Publishing 1 publication, 5.56%
Wiley	Wiley, 1, 5.56% Wiley 1 publication, 5.56%
Springer Nature	Springer Nature, 1, 5.56% Springer Nature 1 publication, 5.56%
Annual Reviews	Annual Reviews, 1, 5.56% Annual Reviews 1 publication, 5.56%
Multidisciplinary Digital Publishing Institute (MDPI)	Multidisciplinary Digital Publishing Institute (MDPI), 1, 5.56% Multidisciplinary Digital Publishing Institute (MDPI) 1 publication, 5.56%
Royal Society of Chemistry (RSC)	Royal Society of Chemistry (RSC), 1, 5.56% Royal Society of Chemistry (RSC) 1 publication, 5.56%
Frontiers Media S.A.	Frontiers Media S.A., 1, 5.56% Frontiers Media S.A. 1 publication, 5.56%
Autonomous Non-profit Organization Editorial Board of the journal Uspekhi Khimii	Autonomous Non-profit Organization Editorial Board of the journal Uspekhi Khimii, 1, 5.56% Autonomous Non-profit Organization Editorial Board of the journal Uspekhi Khimii 1 publication, 5.56%
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Bonilla M. H. et al. Exploring Li-ion conductivity in cubic, tetragonal and mixed-phase Al-substituted Li7La3Zr2O12 using atomistic simulations and effective medium theory // Acta Materialia. 2019. Vol. 175. pp. 426-435.

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Bonilla M. H., García Daza F. A., Carrasco J., Akhmatskaya E. V. Exploring Li-ion conductivity in cubic, tetragonal and mixed-phase Al-substituted Li7La3Zr2O12 using atomistic simulations and effective medium theory // Acta Materialia. 2019. Vol. 175. pp. 426-435.

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RIS Copy

TY - JOUR

DO - 10.1016/j.actamat.2019.06.033

UR - https://doi.org/10.1016/j.actamat.2019.06.033

TI - Exploring Li-ion conductivity in cubic, tetragonal and mixed-phase Al-substituted Li7La3Zr2O12 using atomistic simulations and effective medium theory

T2 - Acta Materialia

AU - Bonilla, Mauricio Hernandez

AU - García Daza, Fabián A.

AU - Carrasco, Javier

AU - Akhmatskaya, Elena V.

PY - 2019

DA - 2019/08/01 00:00:00

PB - Elsevier

SP - 426-435

VL - 175

SN - 1359-6454

ER -

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@article{2019_Bonilla,

author = {Mauricio Hernandez Bonilla and Fabián A. García Daza and Javier Carrasco and Elena V. Akhmatskaya},

title = {Exploring Li-ion conductivity in cubic, tetragonal and mixed-phase Al-substituted Li7La3Zr2O12 using atomistic simulations and effective medium theory},

journal = {Acta Materialia},

year = {2019},

volume = {175},

publisher = {Elsevier},

month = {aug},

url = {https://doi.org/10.1016/j.actamat.2019.06.033},

pages = {426--435},

doi = {10.1016/j.actamat.2019.06.033}

}

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Publisher

Elsevier

Journal

Acta Materialia

Quartile SCImago

Quartile WOS

Impact factor

9.4

ISSN

13596454 (Print)