Halide Substitution Effects on Lithium-Ion Diffusion in Protonated Antiperovskites

Kee Sung Han; J. David Bazak; Robert L. Sacci; Ying Chen; Tyler H. Bennett; Jagjit Nanda; Vijayakumar Murugesan

doi:10.1021/acs.jpcc.2c09097

Halide Substitution Effects on Lithium-Ion Diffusion in Protonated Antiperovskites

Kee Sung Han, J. David Bazak, Robert L. Sacci, Ying Chen, Tyler H. Bennett, Jagjit Nanda, Vijayakumar Murugesan

Energy Storage & Conversion

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

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Abstract

Solid-state electrolytes (SSEs) for all-solid-state lithium-ion batteries are generating intense interest because these batteries can improve the safety and performance compared with devices fabricated with conventional, flammable liquid electrolytes. In these SSEs, it has been suggested that Li⁺ ion diffusion in the grain boundaries is hindered and is a critical determinant of the overall ionic conductivity (σ). However, Li⁺ ion diffusivities in the grain (D_G) and the grain boundary (D_GB) are difficult to determine experimentally, with few techniques capable of distinguishing the individual contributions. Here, we distinguished the D_G and D_GB for the protonated lithium antiperovskites (pLiAPs) SSEs: Li₂OHCl, Li₂OHBr, Li₂OHF_0.1Cl_0.9, Li₂OHF_0.1Br_0.9, and Li₂OHCl_0.37Br_0.63. The measurements were obtained directly from ⁷Li pulsed-field gradient nuclear magnetic resonance (PFG-NMR) at 353 K. The ⁷Li PFG-NMR echo profiles were composed of two primary components with additional secondary oscillatory components - the so-called NMR diffraction phenomenon. The length scale separating the two main components corresponds to a diffusion length of ∼1.7 μm, which is thought to be the average grain size (by diameter). The short-range (≤1.7 μm) diffusion component associated with D_G (≈10^-11 m²/s) varied minimally with halide substitution, while the long-range (≥1.7 μm) component D_GB (≈10^-12 to 10^-15 m²/s) was highly sensitive to the substitution of halides and closely correlated with σ. In addition, from the comparison of the ratio D_GB/D_G to D_τ (the Li⁺ ion diffusion coefficient estimated from the rotational correlation time, τ_c), it was determined that the fractional contribution of D_G to σ is negligible; 0.01-0.04 in the pLiAPs studied here. These insights provide a fundamental understanding of the halide substitution effects on Li⁺ ion grain vs grain boundary diffusion and suggest that careful engineering of the grain boundaries at the microscopic level is necessary to achieve high-performance pLiAP SSEs.

Original language	English
Pages (from-to)	4451-4458
Number of pages	8
Journal	Journal of Physical Chemistry C
Volume	127
Issue number	9
DOIs	https://doi.org/10.1021/acs.jpcc.2c09097
State	Published - Mar 9 2023

Funding

This work is primarily supported by the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), and NMR measurements were accomplished at the Environmental Molecular Sciences Laboratory, a national scientific user facility supported by the Department of Energy′s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. R.L.S. and J.N. acknowledge support from Vehicle Technologies Office (VTO) under the Office of Energy Efficiency and Renewable Energy (EERE) as part of the Battery Materials Research (BMR) program for solid electrolyte materials preparation.

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title = "Halide Substitution Effects on Lithium-Ion Diffusion in Protonated Antiperovskites",

abstract = "Solid-state electrolytes (SSEs) for all-solid-state lithium-ion batteries are generating intense interest because these batteries can improve the safety and performance compared with devices fabricated with conventional, flammable liquid electrolytes. In these SSEs, it has been suggested that Li+ ion diffusion in the grain boundaries is hindered and is a critical determinant of the overall ionic conductivity (σ). However, Li+ ion diffusivities in the grain (DG) and the grain boundary (DGB) are difficult to determine experimentally, with few techniques capable of distinguishing the individual contributions. Here, we distinguished the DG and DGB for the protonated lithium antiperovskites (pLiAPs) SSEs: Li2OHCl, Li2OHBr, Li2OHF0.1Cl0.9, Li2OHF0.1Br0.9, and Li2OHCl0.37Br0.63. The measurements were obtained directly from 7Li pulsed-field gradient nuclear magnetic resonance (PFG-NMR) at 353 K. The 7Li PFG-NMR echo profiles were composed of two primary components with additional secondary oscillatory components - the so-called NMR diffraction phenomenon. The length scale separating the two main components corresponds to a diffusion length of ∼1.7 μm, which is thought to be the average grain size (by diameter). The short-range (≤1.7 μm) diffusion component associated with DG (≈10-11 m2/s) varied minimally with halide substitution, while the long-range (≥1.7 μm) component DGB (≈10-12 to 10-15 m2/s) was highly sensitive to the substitution of halides and closely correlated with σ. In addition, from the comparison of the ratio DGB/DG to Dτ (the Li+ ion diffusion coefficient estimated from the rotational correlation time, τc), it was determined that the fractional contribution of DG to σ is negligible; 0.01-0.04 in the pLiAPs studied here. These insights provide a fundamental understanding of the halide substitution effects on Li+ ion grain vs grain boundary diffusion and suggest that careful engineering of the grain boundaries at the microscopic level is necessary to achieve high-performance pLiAP SSEs.",

author = "Han, {Kee Sung} and Bazak, {J. David} and Sacci, {Robert L.} and Ying Chen and Bennett, {Tyler H.} and Jagjit Nanda and Vijayakumar Murugesan",

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AU - Han, Kee Sung

AU - Bazak, J. David

AU - Sacci, Robert L.

AU - Chen, Ying

AU - Bennett, Tyler H.

AU - Nanda, Jagjit

AU - Murugesan, Vijayakumar

PY - 2023/3/9

Y1 - 2023/3/9

N2 - Solid-state electrolytes (SSEs) for all-solid-state lithium-ion batteries are generating intense interest because these batteries can improve the safety and performance compared with devices fabricated with conventional, flammable liquid electrolytes. In these SSEs, it has been suggested that Li+ ion diffusion in the grain boundaries is hindered and is a critical determinant of the overall ionic conductivity (σ). However, Li+ ion diffusivities in the grain (DG) and the grain boundary (DGB) are difficult to determine experimentally, with few techniques capable of distinguishing the individual contributions. Here, we distinguished the DG and DGB for the protonated lithium antiperovskites (pLiAPs) SSEs: Li2OHCl, Li2OHBr, Li2OHF0.1Cl0.9, Li2OHF0.1Br0.9, and Li2OHCl0.37Br0.63. The measurements were obtained directly from 7Li pulsed-field gradient nuclear magnetic resonance (PFG-NMR) at 353 K. The 7Li PFG-NMR echo profiles were composed of two primary components with additional secondary oscillatory components - the so-called NMR diffraction phenomenon. The length scale separating the two main components corresponds to a diffusion length of ∼1.7 μm, which is thought to be the average grain size (by diameter). The short-range (≤1.7 μm) diffusion component associated with DG (≈10-11 m2/s) varied minimally with halide substitution, while the long-range (≥1.7 μm) component DGB (≈10-12 to 10-15 m2/s) was highly sensitive to the substitution of halides and closely correlated with σ. In addition, from the comparison of the ratio DGB/DG to Dτ (the Li+ ion diffusion coefficient estimated from the rotational correlation time, τc), it was determined that the fractional contribution of DG to σ is negligible; 0.01-0.04 in the pLiAPs studied here. These insights provide a fundamental understanding of the halide substitution effects on Li+ ion grain vs grain boundary diffusion and suggest that careful engineering of the grain boundaries at the microscopic level is necessary to achieve high-performance pLiAP SSEs.

AB - Solid-state electrolytes (SSEs) for all-solid-state lithium-ion batteries are generating intense interest because these batteries can improve the safety and performance compared with devices fabricated with conventional, flammable liquid electrolytes. In these SSEs, it has been suggested that Li+ ion diffusion in the grain boundaries is hindered and is a critical determinant of the overall ionic conductivity (σ). However, Li+ ion diffusivities in the grain (DG) and the grain boundary (DGB) are difficult to determine experimentally, with few techniques capable of distinguishing the individual contributions. Here, we distinguished the DG and DGB for the protonated lithium antiperovskites (pLiAPs) SSEs: Li2OHCl, Li2OHBr, Li2OHF0.1Cl0.9, Li2OHF0.1Br0.9, and Li2OHCl0.37Br0.63. The measurements were obtained directly from 7Li pulsed-field gradient nuclear magnetic resonance (PFG-NMR) at 353 K. The 7Li PFG-NMR echo profiles were composed of two primary components with additional secondary oscillatory components - the so-called NMR diffraction phenomenon. The length scale separating the two main components corresponds to a diffusion length of ∼1.7 μm, which is thought to be the average grain size (by diameter). The short-range (≤1.7 μm) diffusion component associated with DG (≈10-11 m2/s) varied minimally with halide substitution, while the long-range (≥1.7 μm) component DGB (≈10-12 to 10-15 m2/s) was highly sensitive to the substitution of halides and closely correlated with σ. In addition, from the comparison of the ratio DGB/DG to Dτ (the Li+ ion diffusion coefficient estimated from the rotational correlation time, τc), it was determined that the fractional contribution of DG to σ is negligible; 0.01-0.04 in the pLiAPs studied here. These insights provide a fundamental understanding of the halide substitution effects on Li+ ion grain vs grain boundary diffusion and suggest that careful engineering of the grain boundaries at the microscopic level is necessary to achieve high-performance pLiAP SSEs.

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Halide Substitution Effects on Lithium-Ion Diffusion in Protonated Antiperovskites

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