The Key Role of Grain Boundary Dynamics in Revolutionizing the Potential of Solid Electrolytes

Yangyang Wang; Charlotte Thomas; Kaitlin Garman; Hwangsun Kim; Zonghai Chen; Miaofang Chi; Chunmei Ban

doi:10.1002/adfm.202404434

The Key Role of Grain Boundary Dynamics in Revolutionizing the Potential of Solid Electrolytes

Yangyang Wang, Charlotte Thomas, Kaitlin Garman, Hwangsun Kim, Zonghai Chen, Miaofang Chi, Chunmei Ban

electron Microscopy and Microanalysis

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

1 Scopus citations

Abstract

Solid electrolytes (SEs) have the potential to enhance the safety and performance of Li-metal batteries. However, the existence of grain boundaries in polycrystalline SEs presents a significant challenge for both ionic and electronic migration, promoting the propagation of detrimental lithium dendrites. This study compares the roles of grain boundaries in electrical properties of three distinct SEs including garnet-type Li_6.5La₃Zr_1.5Ta_0.5O₁₂ (LLZO), argyrodite-type Li₆PS₅Cl (LPSC), and NASICON-type Li₁₊_x₊_yAl_x(Ti,Ge)_2-_xSi_yP_3-_yO₁₂ (LATP). Results demonstrate that the electronic and ionic conductivities of solid-state electrolytes are affected differently by grain boundaries, depending on the specific type of electrolyte. For instance, LLZO and LATP experience dielectric breakdown at 3.7 and 5.3 V, respectively, while LPSC does not exhibit such behavior. Here, a new chemical modification is proposed that simultaneously alters the composition of both the surface and grain boundaries of SEs, ultimately reducing electronic conductivity for the LLZO SEs. Consequently, the proposed LLZO exhibits unprecedented dendrite-free cycling stability, achieving a remarkable 12 000-h lifetime at room temperature, surpassing conventional strategies such as surface coatings in dendrite mitigation. This study highlights the significance of modifying grain boundaries to design safe and durable Li-metal batteries. It provides new insights for developing SEs that are highly resistant to dendrite formation.

Original language	English
Article number	2404434
Journal	Advanced Functional Materials
Volume	34
Issue number	45
DOIs	https://doi.org/10.1002/adfm.202404434
State	Published - Nov 5 2024

Funding

Y.W, K.G, and C.B thank Michael Mo at KULR Technology Group and acknowledge the funding through KULR AWD-21-08-0023. The CU Boulder authors would like to express their gratitude for the support and suggestions provided by Dr. Aju Jugessur, Dr. Adrian Gestos and Dr. Tomoko Borsa at COSINC. This research was supported in part by the Colorado Shared Instrumentation in Nanofabrication and Characterization (COSINC, RRID: SCR_018985): COSINC-CHR (Characterization), College of Engineering & Applied Science, University of Colorado Boulder. H.K. and M.C. were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. Microscopy studies were partially conducted at the Center for Nanophase Materials Sciences (CNMS), an Office of Science User Facility at Oak Ridge National Laboratory. Research at Argonne National Laboratory was supported by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Argonne National Laboratory is operated\u00A0for the DOE Office of Science by UChicago Argonne, LLC, under Contract DE-AC02-06CH11357. Y.W, K.G, and C.B thank Michael Mo at KULR Technology Group and acknowledge the funding through KULR AWD\u201021\u201008\u20100023. The CU Boulder authors would like to express their gratitude for the support and suggestions provided by Dr. Aju Jugessur, Dr. Adrian Gestos and Dr. Tomoko Borsa at COSINC. This research was supported in part by the Colorado Shared Instrumentation in Nanofabrication and Characterization (COSINC, RRID: SCR_018985): COSINC\u2010CHR (Characterization), College of Engineering & Applied Science, University of Colorado Boulder. H.K. and M.C. were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. Microscopy studies were partially conducted at the Center for Nanophase Materials Sciences (CNMS), an Office of Science User Facility at Oak Ridge National Laboratory. Research at Argonne National Laboratory was supported by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Argonne National Laboratory is operated for the DOE Office of Science by UChicago Argonne, LLC, under Contract DE\u2010AC02\u201006CH11357.

Funders	Funder number
Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office
Basic Energy Sciences
Division of Materials Sciences and Engineering
College of Engineering & Applied Science, University of Colorado Boulder
Oak Ridge National Laboratory
U.S. Department of Energy
Argonne National Laboratory
KULR	AWD-21-08-0023
University of Colorado Boulder	SCR_018985
Office of Science	DE‐AC02‐06CH11357

Keywords

electronic and ionic conductivity
energy storage
fluorination
grain boundaries
solid-state batteries
solid-state electrolytes
surface modification

UN SDGs

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

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10.1002/adfm.202404434

Cite this

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abstract = "Solid electrolytes (SEs) have the potential to enhance the safety and performance of Li-metal batteries. However, the existence of grain boundaries in polycrystalline SEs presents a significant challenge for both ionic and electronic migration, promoting the propagation of detrimental lithium dendrites. This study compares the roles of grain boundaries in electrical properties of three distinct SEs including garnet-type Li6.5La3Zr1.5Ta0.5O12 (LLZO), argyrodite-type Li6PS5Cl (LPSC), and NASICON-type Li1+x+yAlx(Ti,Ge)2-xSiyP3-yO12 (LATP). Results demonstrate that the electronic and ionic conductivities of solid-state electrolytes are affected differently by grain boundaries, depending on the specific type of electrolyte. For instance, LLZO and LATP experience dielectric breakdown at 3.7 and 5.3 V, respectively, while LPSC does not exhibit such behavior. Here, a new chemical modification is proposed that simultaneously alters the composition of both the surface and grain boundaries of SEs, ultimately reducing electronic conductivity for the LLZO SEs. Consequently, the proposed LLZO exhibits unprecedented dendrite-free cycling stability, achieving a remarkable 12 000-h lifetime at room temperature, surpassing conventional strategies such as surface coatings in dendrite mitigation. This study highlights the significance of modifying grain boundaries to design safe and durable Li-metal batteries. It provides new insights for developing SEs that are highly resistant to dendrite formation.",

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N2 - Solid electrolytes (SEs) have the potential to enhance the safety and performance of Li-metal batteries. However, the existence of grain boundaries in polycrystalline SEs presents a significant challenge for both ionic and electronic migration, promoting the propagation of detrimental lithium dendrites. This study compares the roles of grain boundaries in electrical properties of three distinct SEs including garnet-type Li6.5La3Zr1.5Ta0.5O12 (LLZO), argyrodite-type Li6PS5Cl (LPSC), and NASICON-type Li1+x+yAlx(Ti,Ge)2-xSiyP3-yO12 (LATP). Results demonstrate that the electronic and ionic conductivities of solid-state electrolytes are affected differently by grain boundaries, depending on the specific type of electrolyte. For instance, LLZO and LATP experience dielectric breakdown at 3.7 and 5.3 V, respectively, while LPSC does not exhibit such behavior. Here, a new chemical modification is proposed that simultaneously alters the composition of both the surface and grain boundaries of SEs, ultimately reducing electronic conductivity for the LLZO SEs. Consequently, the proposed LLZO exhibits unprecedented dendrite-free cycling stability, achieving a remarkable 12 000-h lifetime at room temperature, surpassing conventional strategies such as surface coatings in dendrite mitigation. This study highlights the significance of modifying grain boundaries to design safe and durable Li-metal batteries. It provides new insights for developing SEs that are highly resistant to dendrite formation.

AB - Solid electrolytes (SEs) have the potential to enhance the safety and performance of Li-metal batteries. However, the existence of grain boundaries in polycrystalline SEs presents a significant challenge for both ionic and electronic migration, promoting the propagation of detrimental lithium dendrites. This study compares the roles of grain boundaries in electrical properties of three distinct SEs including garnet-type Li6.5La3Zr1.5Ta0.5O12 (LLZO), argyrodite-type Li6PS5Cl (LPSC), and NASICON-type Li1+x+yAlx(Ti,Ge)2-xSiyP3-yO12 (LATP). Results demonstrate that the electronic and ionic conductivities of solid-state electrolytes are affected differently by grain boundaries, depending on the specific type of electrolyte. For instance, LLZO and LATP experience dielectric breakdown at 3.7 and 5.3 V, respectively, while LPSC does not exhibit such behavior. Here, a new chemical modification is proposed that simultaneously alters the composition of both the surface and grain boundaries of SEs, ultimately reducing electronic conductivity for the LLZO SEs. Consequently, the proposed LLZO exhibits unprecedented dendrite-free cycling stability, achieving a remarkable 12 000-h lifetime at room temperature, surpassing conventional strategies such as surface coatings in dendrite mitigation. This study highlights the significance of modifying grain boundaries to design safe and durable Li-metal batteries. It provides new insights for developing SEs that are highly resistant to dendrite formation.

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The Key Role of Grain Boundary Dynamics in Revolutionizing the Potential of Solid Electrolytes

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Keywords

UN SDGs

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