Li Dynamics in Mixed Ionic-Electronic Conducting Interlayer of All-Solid-State Li-metal Batteries

Daxian Cao; Yuxuan Zhang; Tongtai Ji; Xianhui Zhao; Ercan Cakmak; Soydan Ozcan; Michael Geiwitz; Jean Bilheux; Kang Xu; Ying Wang; Kenneth Stephen Burch; Qingsong Howard Tu; Hongli Zhu

doi:10.1021/acs.nanolett.3c04072

Li Dynamics in Mixed Ionic-Electronic Conducting Interlayer of All-Solid-State Li-metal Batteries

Daxian Cao, Yuxuan Zhang, Tongtai Ji, Xianhui Zhao, Ercan Cakmak, Soydan Ozcan, Michael Geiwitz, Jean Bilheux, Kang Xu, Ying Wang, Kenneth Stephen Burch, Qingsong Howard Tu, Hongli Zhu

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

1 Scopus citations

Abstract

Lithium-metal (Li⁰) anodes potentially enable all-solid-state batteries with high energy density. However, it shows incompatibility with sulfide solid-state electrolytes (SEs). One strategy is introducing an interlayer, generally made of a mixed ionic-electronic conductor (MIEC). Yet, how Li behaves within MIEC remains unknown. Herein, we investigated the Li dynamics in a graphite interlayer, a typical MIEC, by using operando neutron imaging and Raman spectroscopy. This study revealed that intercalation-extrusion-dominated mechanochemical reactions during cell assembly transform the graphite into a Li-graphite interlayer consisting of SE, Li⁰, and graphite-intercalation compounds. During charging, Li⁺ preferentially deposited at the Li-graphite|SE interface. Upon further plating, Li⁰-dendrites formed, inducing short circuits and the reverse migration of Li⁰. Modeling indicates the interface has the lowest nucleation barrier, governing lithium transport paths. Our study elucidates intricate mechano-chemo-electrochemical processes in mixed conducting interlayers. The behavior of Li⁺ and Li⁰ in the interlayer is governed by multiple competing factors.

Original language	English
Pages (from-to)	1544-1552
Number of pages	9
Journal	Nano Letters
Volume	24
Issue number	5
DOIs	https://doi.org/10.1021/acs.nanolett.3c04072
State	Published - Feb 7 2024

Funding

H.Z. acknowledges the financial support received from Office of Science Department of Energy under Award Number DE-SC0024528. This research used resources at the High Flux Isotope Reactor, a DOE Office of Science User Facility operated by Oak Ridge National Laboratory. The authors acknowledge the Northeastern University Center for Renewable Energy Technology for access to the SEM and XRD equipment. The work of M.G. was supported by the National Science Foundation via the award DMR-2003343. K.S.B. acknowledges the primary support of the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences under award number DE-SC0018675.

Keywords

Raman spectroscopy
all-solid-state batteries
lithium−metal anode
mechano-chemo-electrochemical processes
mixed ionic-electronic conductor (MIEC)
operando neutron imaging

UN SDGs

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

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10.1021/acs.nanolett.3c04072

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title = "Li Dynamics in Mixed Ionic-Electronic Conducting Interlayer of All-Solid-State Li-metal Batteries",

abstract = "Lithium-metal (Li0) anodes potentially enable all-solid-state batteries with high energy density. However, it shows incompatibility with sulfide solid-state electrolytes (SEs). One strategy is introducing an interlayer, generally made of a mixed ionic-electronic conductor (MIEC). Yet, how Li behaves within MIEC remains unknown. Herein, we investigated the Li dynamics in a graphite interlayer, a typical MIEC, by using operando neutron imaging and Raman spectroscopy. This study revealed that intercalation-extrusion-dominated mechanochemical reactions during cell assembly transform the graphite into a Li-graphite interlayer consisting of SE, Li0, and graphite-intercalation compounds. During charging, Li+ preferentially deposited at the Li-graphite|SE interface. Upon further plating, Li0-dendrites formed, inducing short circuits and the reverse migration of Li0. Modeling indicates the interface has the lowest nucleation barrier, governing lithium transport paths. Our study elucidates intricate mechano-chemo-electrochemical processes in mixed conducting interlayers. The behavior of Li+ and Li0 in the interlayer is governed by multiple competing factors.",

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author = "Daxian Cao and Yuxuan Zhang and Tongtai Ji and Xianhui Zhao and Ercan Cakmak and Soydan Ozcan and Michael Geiwitz and Jean Bilheux and Kang Xu and Ying Wang and Burch, {Kenneth Stephen} and Tu, {Qingsong Howard} and Hongli Zhu",

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AU - Cao, Daxian

AU - Zhang, Yuxuan

AU - Ji, Tongtai

AU - Zhao, Xianhui

AU - Cakmak, Ercan

AU - Ozcan, Soydan

AU - Geiwitz, Michael

AU - Bilheux, Jean

AU - Xu, Kang

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AU - Burch, Kenneth Stephen

AU - Tu, Qingsong Howard

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AB - Lithium-metal (Li0) anodes potentially enable all-solid-state batteries with high energy density. However, it shows incompatibility with sulfide solid-state electrolytes (SEs). One strategy is introducing an interlayer, generally made of a mixed ionic-electronic conductor (MIEC). Yet, how Li behaves within MIEC remains unknown. Herein, we investigated the Li dynamics in a graphite interlayer, a typical MIEC, by using operando neutron imaging and Raman spectroscopy. This study revealed that intercalation-extrusion-dominated mechanochemical reactions during cell assembly transform the graphite into a Li-graphite interlayer consisting of SE, Li0, and graphite-intercalation compounds. During charging, Li+ preferentially deposited at the Li-graphite|SE interface. Upon further plating, Li0-dendrites formed, inducing short circuits and the reverse migration of Li0. Modeling indicates the interface has the lowest nucleation barrier, governing lithium transport paths. Our study elucidates intricate mechano-chemo-electrochemical processes in mixed conducting interlayers. The behavior of Li+ and Li0 in the interlayer is governed by multiple competing factors.

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Li Dynamics in Mixed Ionic-Electronic Conducting Interlayer of All-Solid-State Li-metal Batteries

Abstract

Funding

Keywords

UN SDGs

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