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Nanoscale Ion Transport Enhances Conductivity in Solid Polymer-Ceramic Lithium Electrolytes
Abstract
The predictive design of flexible and solvent-free polymer electrolytes for solid-state batteries requires an understanding of the fundamental principles governing the ion transport. In this work, we establish a correlation among the composite structures, polymer segmental dynamics, and lithium ion (Li+) transport in a ceramic-polymer composite. Elucidating this structure–property relationship will allow tailoring of the Li+ conductivity by optimizing the macroscopic electrochemical stability of the electrolyte. The ion dissociation from the slow polymer segmental dynamics was found to be enhanced by controlling the morphology and functionality of the polymer/ceramic interface. The chemical structure of the Li+ salt in the composite electrolyte was correlated with the size of the ionic cluster domains, the conductivity mechanism, and the electrochemical stability of the electrolyte. Polyethylene oxide (PEO) filled with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or lithium bis(fluorosulfonyl) imide (LiFSI) salts was used as a matrix. A garnet electrolyte, aluminum substituted lithium lanthanum zirconium oxide (Al-LLZO) with a planar geometry, was used for the ceramic nanoparticle moieties. Further, the dynamics of the strongly bound and highly mobile Li+ were investigated using dielectric relaxation spectroscopy. The incorporation of the Al-LLZO platelets increased the number density of more mobile Li+. The structure of the nanoscale ion-agglomeration was investigatedmore »
- Authors:
-
[1];
[1];
[2];
[1];
[1];
[1];
[2];
[1]
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 2283877
- Grant/Contract Number:
- AC05-00OR22725; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Nano
- Additional Journal Information:
- Journal Volume: 18; Journal Issue: 4; Journal ID: ISSN 1936-0851
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; polymer electrolyte; lithium bis(trifluoromethanesulfonyl)imide (LiTFSI); lithium bis(fluorosulfonyl) imide (LiFSI); aluminum substituted lithium lanthanum zirconium oxide; solid-state batteries
Citation Formats
Polizos, Georgios, Goswami, Monojoy, Keum, Jong K., He, Lilin, Jafta, Charl J., Sharma, Jaswinder, Wang, Yangyang, Kearney, Logan T., Tao, Runming, and Li, Jianlin. Nanoscale Ion Transport Enhances Conductivity in Solid Polymer-Ceramic Lithium Electrolytes. United States: N. p., 2024.
Web. doi:10.1021/acsnano.3c03901.
Polizos, Georgios, Goswami, Monojoy, Keum, Jong K., He, Lilin, Jafta, Charl J., Sharma, Jaswinder, Wang, Yangyang, Kearney, Logan T., Tao, Runming, & Li, Jianlin. Nanoscale Ion Transport Enhances Conductivity in Solid Polymer-Ceramic Lithium Electrolytes. United States. https://doi.org/10.1021/acsnano.3c03901
Polizos, Georgios, Goswami, Monojoy, Keum, Jong K., He, Lilin, Jafta, Charl J., Sharma, Jaswinder, Wang, Yangyang, Kearney, Logan T., Tao, Runming, and Li, Jianlin. Thu .
"Nanoscale Ion Transport Enhances Conductivity in Solid Polymer-Ceramic Lithium Electrolytes". United States. https://doi.org/10.1021/acsnano.3c03901.
@article{osti_2283877,
title = {Nanoscale Ion Transport Enhances Conductivity in Solid Polymer-Ceramic Lithium Electrolytes},
author = {Polizos, Georgios and Goswami, Monojoy and Keum, Jong K. and He, Lilin and Jafta, Charl J. and Sharma, Jaswinder and Wang, Yangyang and Kearney, Logan T. and Tao, Runming and Li, Jianlin},
abstractNote = {The predictive design of flexible and solvent-free polymer electrolytes for solid-state batteries requires an understanding of the fundamental principles governing the ion transport. In this work, we establish a correlation among the composite structures, polymer segmental dynamics, and lithium ion (Li+) transport in a ceramic-polymer composite. Elucidating this structure–property relationship will allow tailoring of the Li+ conductivity by optimizing the macroscopic electrochemical stability of the electrolyte. The ion dissociation from the slow polymer segmental dynamics was found to be enhanced by controlling the morphology and functionality of the polymer/ceramic interface. The chemical structure of the Li+ salt in the composite electrolyte was correlated with the size of the ionic cluster domains, the conductivity mechanism, and the electrochemical stability of the electrolyte. Polyethylene oxide (PEO) filled with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or lithium bis(fluorosulfonyl) imide (LiFSI) salts was used as a matrix. A garnet electrolyte, aluminum substituted lithium lanthanum zirconium oxide (Al-LLZO) with a planar geometry, was used for the ceramic nanoparticle moieties. Further, the dynamics of the strongly bound and highly mobile Li+ were investigated using dielectric relaxation spectroscopy. The incorporation of the Al-LLZO platelets increased the number density of more mobile Li+. The structure of the nanoscale ion-agglomeration was investigated by small-angle X-ray scattering, while molecular dynamics (MD) simulation studies were conducted to obtain the fundamental mechanism of the decorrelation of the Li+ in the LiTFSI and LiFSI salts from the long PEO chain.},
doi = {10.1021/acsnano.3c03901},
journal = {ACS Nano},
number = 4,
volume = 18,
place = {United States},
year = {Thu Jan 04 00:00:00 EST 2024},
month = {Thu Jan 04 00:00:00 EST 2024}
}
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