Yttrium Contenting Compositionally Complex Medium-Entropy Li-Garnet Electrolyte with Improved Ionic Conductivity

Chang Li; Nava Raj Giri; Yan Chen; Fernando A. Soto; Zhezhen Fu

doi:10.1021/acsami.5c10130

Yttrium Contenting Compositionally Complex Medium-Entropy Li-Garnet Electrolyte with Improved Ionic Conductivity

Chang Li
, Nava Raj Giri
, Yan Chen
, Fernando A. Soto
, Zhezhen Fu

Materials Engineering

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

2 Scopus citations

Abstract

The compositionally complex medium/high-entropy design concept can greatly expand the categories and affect the properties of the materials. With such a designing concept, a medium-entropy Li-garnet electrolyte with appropriate yttrium content (formula Li_6.6La₃ZrNb_0.3Ta_0.3Hf_0.3Y_0.1O₁₂) shows a record-high ionic conductivity of ∼5.7 × 10^–4 S/cm, the highest reported for any single-site substituted high/medium-entropy Li-garnet. The assembled Li metal symmetric cells also show stable long-term cycling (0.1 mA/cm² for over 200 h). Neutron powder diffraction and Rietveld refinement results indicate that a competing conduction mechanism between (1) occupancy on high mobility of 96h sites and (2) the associated site vacancies and the bond length requires an appropriate content of Y for enhanced ionic conductivity. Li-ion hopping through the bottleneck can also contribute to the conductivity. Density functional theory and Born–Oppenheimer molecular dynamics simulations also indicate the high mobility and number of hopping transitions of Li ions, contributing to the high ionic conductivity.

Original language	English
Pages (from-to)	48267-48278
Number of pages	12
Journal	ACS Applied Materials and Interfaces
Volume	17
Issue number	34
DOIs	https://doi.org/10.1021/acsami.5c10130
State	Published - Aug 27 2025

Funding

This material is based upon work supported by the National Science Foundation under Grant No. CMMI-2347492. 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. The beam time was allocated to VULCAN on proposal number IPTS-32459.1. Partial support by Penn State and Penn State Harrisburg seed grants is also acknowledged.

Keywords

Li-garnet
Li-ion conduction mechanisms
Y doping
compositionally complex ceramics
high/medium-entropy ceramics
solid-state electrolytes

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10.1021/acsami.5c10130

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title = "Yttrium Contenting Compositionally Complex Medium-Entropy Li-Garnet Electrolyte with Improved Ionic Conductivity",

abstract = "The compositionally complex medium/high-entropy design concept can greatly expand the categories and affect the properties of the materials. With such a designing concept, a medium-entropy Li-garnet electrolyte with appropriate yttrium content (formula Li6.6La3ZrNb0.3Ta0.3Hf0.3Y0.1O12) shows a record-high ionic conductivity of ∼5.7 × 10–4 S/cm, the highest reported for any single-site substituted high/medium-entropy Li-garnet. The assembled Li metal symmetric cells also show stable long-term cycling (0.1 mA/cm2 for over 200 h). Neutron powder diffraction and Rietveld refinement results indicate that a competing conduction mechanism between (1) occupancy on high mobility of 96h sites and (2) the associated site vacancies and the bond length requires an appropriate content of Y for enhanced ionic conductivity. Li-ion hopping through the bottleneck can also contribute to the conductivity. Density functional theory and Born–Oppenheimer molecular dynamics simulations also indicate the high mobility and number of hopping transitions of Li ions, contributing to the high ionic conductivity.",

keywords = "Li-garnet, Li-ion conduction mechanisms, Y doping, compositionally complex ceramics, high/medium-entropy ceramics, solid-state electrolytes",

author = "Chang Li and Giri, \{Nava Raj\} and Yan Chen and Soto, \{Fernando A.\} and Zhezhen Fu",

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year = "2025",

month = aug,

day = "27",

doi = "10.1021/acsami.5c10130",

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volume = "17",

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T1 - Yttrium Contenting Compositionally Complex Medium-Entropy Li-Garnet Electrolyte with Improved Ionic Conductivity

AU - Li, Chang

AU - Giri, Nava Raj

AU - Chen, Yan

AU - Soto, Fernando A.

AU - Fu, Zhezhen

PY - 2025/8/27

Y1 - 2025/8/27

N2 - The compositionally complex medium/high-entropy design concept can greatly expand the categories and affect the properties of the materials. With such a designing concept, a medium-entropy Li-garnet electrolyte with appropriate yttrium content (formula Li6.6La3ZrNb0.3Ta0.3Hf0.3Y0.1O12) shows a record-high ionic conductivity of ∼5.7 × 10–4 S/cm, the highest reported for any single-site substituted high/medium-entropy Li-garnet. The assembled Li metal symmetric cells also show stable long-term cycling (0.1 mA/cm2 for over 200 h). Neutron powder diffraction and Rietveld refinement results indicate that a competing conduction mechanism between (1) occupancy on high mobility of 96h sites and (2) the associated site vacancies and the bond length requires an appropriate content of Y for enhanced ionic conductivity. Li-ion hopping through the bottleneck can also contribute to the conductivity. Density functional theory and Born–Oppenheimer molecular dynamics simulations also indicate the high mobility and number of hopping transitions of Li ions, contributing to the high ionic conductivity.

AB - The compositionally complex medium/high-entropy design concept can greatly expand the categories and affect the properties of the materials. With such a designing concept, a medium-entropy Li-garnet electrolyte with appropriate yttrium content (formula Li6.6La3ZrNb0.3Ta0.3Hf0.3Y0.1O12) shows a record-high ionic conductivity of ∼5.7 × 10–4 S/cm, the highest reported for any single-site substituted high/medium-entropy Li-garnet. The assembled Li metal symmetric cells also show stable long-term cycling (0.1 mA/cm2 for over 200 h). Neutron powder diffraction and Rietveld refinement results indicate that a competing conduction mechanism between (1) occupancy on high mobility of 96h sites and (2) the associated site vacancies and the bond length requires an appropriate content of Y for enhanced ionic conductivity. Li-ion hopping through the bottleneck can also contribute to the conductivity. Density functional theory and Born–Oppenheimer molecular dynamics simulations also indicate the high mobility and number of hopping transitions of Li ions, contributing to the high ionic conductivity.

KW - Li-garnet

KW - Li-ion conduction mechanisms

KW - Y doping

KW - compositionally complex ceramics

KW - high/medium-entropy ceramics

KW - solid-state electrolytes

UR - https://www.scopus.com/pages/publications/105014463801

U2 - 10.1021/acsami.5c10130

DO - 10.1021/acsami.5c10130

M3 - Article

C2 - 40824312

AN - SCOPUS:105014463801

SN - 1944-8244

VL - 17

SP - 48267

EP - 48278

JO - ACS Applied Materials and Interfaces

JF - ACS Applied Materials and Interfaces

IS - 34

ER -

Yttrium Contenting Compositionally Complex Medium-Entropy Li-Garnet Electrolyte with Improved Ionic Conductivity

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