A self-healing plastic ceramic electrolyte by an aprotic dynamic polymer network for lithium metal batteries

Abstract Oxide ceramic electrolytes (OCEs) have great potential for solid-state lithium metal (Li0) battery applications because, in theory, their high elastic modulus provides better resistance to Li0 dendrite growth. However, in practice, OCEs can hardly survive critical current densities higher t...

Full description

Saved in:
Bibliographic Details
Main Authors: Yubin He, Chunyang Wang, Rui Zhang, Peichao Zou, Zhouyi Chen, Seong-Min Bak, Stephen E. Trask, Yonghua Du, Ruoqian Lin, Enyuan Hu, Huolin L. Xin
Format: Article
Language:English
Published: Nature Portfolio 2024-11-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-024-53869-z
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1850163056102866944
author Yubin He
Chunyang Wang
Rui Zhang
Peichao Zou
Zhouyi Chen
Seong-Min Bak
Stephen E. Trask
Yonghua Du
Ruoqian Lin
Enyuan Hu
Huolin L. Xin
author_facet Yubin He
Chunyang Wang
Rui Zhang
Peichao Zou
Zhouyi Chen
Seong-Min Bak
Stephen E. Trask
Yonghua Du
Ruoqian Lin
Enyuan Hu
Huolin L. Xin
author_sort Yubin He
collection DOAJ
description Abstract Oxide ceramic electrolytes (OCEs) have great potential for solid-state lithium metal (Li0) battery applications because, in theory, their high elastic modulus provides better resistance to Li0 dendrite growth. However, in practice, OCEs can hardly survive critical current densities higher than 1 mA/cm2. Key issues that contribute to the breakdown of OCEs include Li0 penetration promoted by grain boundaries (GBs), uncontrolled side reactions at electrode-OCE interfaces, and, equally importantly, defects evolution (e.g., void growth and crack propagation) that leads to local current concentration and mechanical failure inside and on OCEs. Here, taking advantage of a dynamically crosslinked aprotic polymer with non-covalent –CH3⋯CF3 bonds, we developed a plastic ceramic electrolyte (PCE) by hybridizing the polymer framework with ionically conductive ceramics. Using in-situ synchrotron X-ray technique and Cryogenic transmission electron microscopy (Cryo-TEM), we uncover that the PCE exhibits self-healing/repairing capability through a two-step dynamic defects removal mechanism. This significantly suppresses the generation of hotspots for Li0 penetration and chemomechanical degradations, resulting in durability beyond 2000 hours in Li0-Li0 cells at 1 mA/cm2. Furthermore, by introducing a polyacrylate buffer layer between PCE and Li0-anode, long cycle life >3600 cycles was achieved when paired with a 4.2 V zero-strain cathode, all under near-zero stack pressure.
format Article
id doaj-art-e6ffcc703e8441d6a1dfd7bd26652a3e
institution OA Journals
issn 2041-1723
language English
publishDate 2024-11-01
publisher Nature Portfolio
record_format Article
series Nature Communications
spelling doaj-art-e6ffcc703e8441d6a1dfd7bd26652a3e2025-08-20T02:22:24ZengNature PortfolioNature Communications2041-17232024-11-0115111310.1038/s41467-024-53869-zA self-healing plastic ceramic electrolyte by an aprotic dynamic polymer network for lithium metal batteriesYubin He0Chunyang Wang1Rui Zhang2Peichao Zou3Zhouyi Chen4Seong-Min Bak5Stephen E. Trask6Yonghua Du7Ruoqian Lin8Enyuan Hu9Huolin L. Xin10Department of Physics and Astronomy, University of CaliforniaDepartment of Physics and Astronomy, University of CaliforniaDepartment of Physics and Astronomy, University of CaliforniaDepartment of Physics and Astronomy, University of CaliforniaDepartment of Physics and Astronomy, University of CaliforniaNational Synchrotron Light Source II, Brookhaven National LaboratoryCell Analysis, Modeling, and Prototyping Facility, Argonne National LaboratoryNational Synchrotron Light Source II, Brookhaven National LaboratoryDepartment of Mechanical Engineering, University of CaliforniaChemistry Division, Brookhaven National LaboratoryDepartment of Physics and Astronomy, University of CaliforniaAbstract Oxide ceramic electrolytes (OCEs) have great potential for solid-state lithium metal (Li0) battery applications because, in theory, their high elastic modulus provides better resistance to Li0 dendrite growth. However, in practice, OCEs can hardly survive critical current densities higher than 1 mA/cm2. Key issues that contribute to the breakdown of OCEs include Li0 penetration promoted by grain boundaries (GBs), uncontrolled side reactions at electrode-OCE interfaces, and, equally importantly, defects evolution (e.g., void growth and crack propagation) that leads to local current concentration and mechanical failure inside and on OCEs. Here, taking advantage of a dynamically crosslinked aprotic polymer with non-covalent –CH3⋯CF3 bonds, we developed a plastic ceramic electrolyte (PCE) by hybridizing the polymer framework with ionically conductive ceramics. Using in-situ synchrotron X-ray technique and Cryogenic transmission electron microscopy (Cryo-TEM), we uncover that the PCE exhibits self-healing/repairing capability through a two-step dynamic defects removal mechanism. This significantly suppresses the generation of hotspots for Li0 penetration and chemomechanical degradations, resulting in durability beyond 2000 hours in Li0-Li0 cells at 1 mA/cm2. Furthermore, by introducing a polyacrylate buffer layer between PCE and Li0-anode, long cycle life >3600 cycles was achieved when paired with a 4.2 V zero-strain cathode, all under near-zero stack pressure.https://doi.org/10.1038/s41467-024-53869-z
spellingShingle Yubin He
Chunyang Wang
Rui Zhang
Peichao Zou
Zhouyi Chen
Seong-Min Bak
Stephen E. Trask
Yonghua Du
Ruoqian Lin
Enyuan Hu
Huolin L. Xin
A self-healing plastic ceramic electrolyte by an aprotic dynamic polymer network for lithium metal batteries
Nature Communications
title A self-healing plastic ceramic electrolyte by an aprotic dynamic polymer network for lithium metal batteries
title_full A self-healing plastic ceramic electrolyte by an aprotic dynamic polymer network for lithium metal batteries
title_fullStr A self-healing plastic ceramic electrolyte by an aprotic dynamic polymer network for lithium metal batteries
title_full_unstemmed A self-healing plastic ceramic electrolyte by an aprotic dynamic polymer network for lithium metal batteries
title_short A self-healing plastic ceramic electrolyte by an aprotic dynamic polymer network for lithium metal batteries
title_sort self healing plastic ceramic electrolyte by an aprotic dynamic polymer network for lithium metal batteries
url https://doi.org/10.1038/s41467-024-53869-z
work_keys_str_mv AT yubinhe aselfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT chunyangwang aselfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT ruizhang aselfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT peichaozou aselfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT zhouyichen aselfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT seongminbak aselfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT stephenetrask aselfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT yonghuadu aselfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT ruoqianlin aselfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT enyuanhu aselfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT huolinlxin aselfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT yubinhe selfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT chunyangwang selfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT ruizhang selfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT peichaozou selfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT zhouyichen selfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT seongminbak selfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT stephenetrask selfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT yonghuadu selfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT ruoqianlin selfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT enyuanhu selfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries
AT huolinlxin selfhealingplasticceramicelectrolytebyanaproticdynamicpolymernetworkforlithiummetalbatteries