Li3-xZrx(Ho/Lu)1-xCl6 Solid Electrolytes Enable Ultrahigh-Loading Solid-State Batteries with a Prelithiated Si Anode

Laidong Zhou; Tongtong Zuo; Chang Li; Qiang Zhang; Jürgen Janek; Linda F. Nazar

doi:10.1021/acsenergylett.3c00763

Li_3-xZr_x(Ho/Lu)_1-xCl₆ Solid Electrolytes Enable Ultrahigh-Loading Solid-State Batteries with a Prelithiated Si Anode

Laidong Zhou
, Tongtong Zuo
, Chang Li
, Qiang Zhang
, Jürgen Janek
, Linda F. Nazar

Powder Diffraction

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

68 Scopus citations

Abstract

We report two new families of lithium metal chloride solid electrolytes Li_3-xZr_x(M)_1-xCl₆ (0 ≤ x ≤ 0.8; M = Ho or Lu) with ionic conductivities of up to 1.8 mS cm^-1 and a low activation energy of 0.34 eV. Structural elucidation via high-resolution neutron diffraction determines the Li ion distribution in trigonal Li₃HoCl₆, orthorhombic-I Li₃LuCl₆, and orthorhombic-II Li_2.4Zr_0.6(Ho/Lu)_0.4Cl₆. The last compound exhibits well-connected Li-ion pathways and abundant Li-ion carriers/vacancies to promote diffusion. All-solid-state batteries with Li_2.6Zr_0.4(Ho/Lu)_0.6Cl₆ solid electrolytes and NCM85 cathodes exhibit stable cycling up to 4.6 V vs Li⁺/Li, which is even preserved up to 4.8 V. Stable cathode interphases are formed for both electrolytes upon cycling to 4.3, 4.6, and 4.8 V cutoff potentials, as identified by a ToF-SIMS analysis. Solid-state cells with a prelithiated Li_0.7Si anode exhibit a significantly increased initial coulombic efficiency of 94.5% compared to Si and a high areal capacity of up to 16.3

Original language	English
Pages (from-to)	3102-3111
Number of pages	10
Journal	ACS Energy Letters
Volume	8
Issue number	7
DOIs	https://doi.org/10.1021/acsenergylett.3c00763
State	Published - Jul 14 2023

Funding

L.F.N. gratefully acknowledges the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences, and NSERC via their Canada Research Chair, Discovery Grant and the Ontario Research Fund (ORF-RE) programs for financial support. The neutron diffraction measurements at the POWGEN instrument at Oak Ridge National Laboratory, Spallation Neutron Source, were sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, US Department of Energy. J.J. gratefully acknowledges funding within the projects CATSE (German-US program by BMBF and DOE) and 03XP0430A (with BMBF cluster FESTBATT; Bundesministerium für Bildung und Forschung). 2

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@article{01c1cd6984d944898ec259ee5a6c76d5,

title = "Li3-xZrx(Ho/Lu)1-xCl6 Solid Electrolytes Enable Ultrahigh-Loading Solid-State Batteries with a Prelithiated Si Anode",

abstract = "We report two new families of lithium metal chloride solid electrolytes Li3-xZrx(M)1-xCl6 (0 ≤ x ≤ 0.8; M = Ho or Lu) with ionic conductivities of up to 1.8 mS cm-1 and a low activation energy of 0.34 eV. Structural elucidation via high-resolution neutron diffraction determines the Li ion distribution in trigonal Li3HoCl6, orthorhombic-I Li3LuCl6, and orthorhombic-II Li2.4Zr0.6(Ho/Lu)0.4Cl6. The last compound exhibits well-connected Li-ion pathways and abundant Li-ion carriers/vacancies to promote diffusion. All-solid-state batteries with Li2.6Zr0.4(Ho/Lu)0.6Cl6 solid electrolytes and NCM85 cathodes exhibit stable cycling up to 4.6 V vs Li+/Li, which is even preserved up to 4.8 V. Stable cathode interphases are formed for both electrolytes upon cycling to 4.3, 4.6, and 4.8 V cutoff potentials, as identified by a ToF-SIMS analysis. Solid-state cells with a prelithiated Li0.7Si anode exhibit a significantly increased initial coulombic efficiency of 94.5\% compared to Si and a high areal capacity of up to 16.3",

author = "Laidong Zhou and Tongtong Zuo and Chang Li and Qiang Zhang and J{\"u}rgen Janek and Nazar, \{Linda F.\}",

note = "Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

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doi = "10.1021/acsenergylett.3c00763",

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T1 - Li3-xZrx(Ho/Lu)1-xCl6 Solid Electrolytes Enable Ultrahigh-Loading Solid-State Batteries with a Prelithiated Si Anode

AU - Zhou, Laidong

AU - Zuo, Tongtong

AU - Li, Chang

AU - Zhang, Qiang

AU - Janek, Jürgen

AU - Nazar, Linda F.

PY - 2023/7/14

Y1 - 2023/7/14

N2 - We report two new families of lithium metal chloride solid electrolytes Li3-xZrx(M)1-xCl6 (0 ≤ x ≤ 0.8; M = Ho or Lu) with ionic conductivities of up to 1.8 mS cm-1 and a low activation energy of 0.34 eV. Structural elucidation via high-resolution neutron diffraction determines the Li ion distribution in trigonal Li3HoCl6, orthorhombic-I Li3LuCl6, and orthorhombic-II Li2.4Zr0.6(Ho/Lu)0.4Cl6. The last compound exhibits well-connected Li-ion pathways and abundant Li-ion carriers/vacancies to promote diffusion. All-solid-state batteries with Li2.6Zr0.4(Ho/Lu)0.6Cl6 solid electrolytes and NCM85 cathodes exhibit stable cycling up to 4.6 V vs Li+/Li, which is even preserved up to 4.8 V. Stable cathode interphases are formed for both electrolytes upon cycling to 4.3, 4.6, and 4.8 V cutoff potentials, as identified by a ToF-SIMS analysis. Solid-state cells with a prelithiated Li0.7Si anode exhibit a significantly increased initial coulombic efficiency of 94.5% compared to Si and a high areal capacity of up to 16.3

AB - We report two new families of lithium metal chloride solid electrolytes Li3-xZrx(M)1-xCl6 (0 ≤ x ≤ 0.8; M = Ho or Lu) with ionic conductivities of up to 1.8 mS cm-1 and a low activation energy of 0.34 eV. Structural elucidation via high-resolution neutron diffraction determines the Li ion distribution in trigonal Li3HoCl6, orthorhombic-I Li3LuCl6, and orthorhombic-II Li2.4Zr0.6(Ho/Lu)0.4Cl6. The last compound exhibits well-connected Li-ion pathways and abundant Li-ion carriers/vacancies to promote diffusion. All-solid-state batteries with Li2.6Zr0.4(Ho/Lu)0.6Cl6 solid electrolytes and NCM85 cathodes exhibit stable cycling up to 4.6 V vs Li+/Li, which is even preserved up to 4.8 V. Stable cathode interphases are formed for both electrolytes upon cycling to 4.3, 4.6, and 4.8 V cutoff potentials, as identified by a ToF-SIMS analysis. Solid-state cells with a prelithiated Li0.7Si anode exhibit a significantly increased initial coulombic efficiency of 94.5% compared to Si and a high areal capacity of up to 16.3

UR - https://www.scopus.com/pages/publications/85164456001

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DO - 10.1021/acsenergylett.3c00763

M3 - Article

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SN - 2380-8195

VL - 8

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JO - ACS Energy Letters

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IS - 7

ER -

Li_3-xZr_x(Ho/Lu)_1-xCl₆ Solid Electrolytes Enable Ultrahigh-Loading Solid-State Batteries with a Prelithiated Si Anode

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