Effect of microphase separation on the limiting current density in hybrid organic-inorganic copolymer electrolytes
Abstract
Hybrid organic-inorganic block copolymer electrolytes are of interest to enable batteries containing lithium metal anodes. The conductive block is a standard polymer electrolyte of poly(ethylene oxide) and the mechanically rigid block is an inorganic poly(acryloisobutyl polyhedral oligomeric silsesquioxane) polymer. Here, in this paper, we compare a poly(acryloisobutyl polyhedral oligomeric silsesquioxane)-b-poly(ethylene oxide)-b-poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (POSS-PEO-POSS) triblock copolymer and a poly(ethylene oxide)-b- poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (PEO-POSS) diblock copolymer mixed with lithium bis(trifluoromethanesulfonyl)imide salt. We have experimentally measured the limiting current density in lithium symmetric cells containing hybrid organic-inorganic electrolytes at 90 °C. The cells were polarized at a large range of applied current density. The diblock copolymer electrolyte exhibited a clear plateau in cell potential at all current densities below the limiting current density. At low applied current density, the triblock copolymer electrolyte also exhibited a clear plateau in cell potential. At currents approaching the limiting current density, the triblock copolymer electrolyte exhibited an underdamped potential profile. The cell potential did not reach a plateau at current densities above the limiting current in both systems. The diblock and triblock copolymer electrolytes were fully characterized using electrochemical methods to determine the ionic conductivity, cation current fraction, salt diffusion coefficient, and openmore »
- Authors:
-
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
- Univ. of California, Berkeley, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division
- Univ. of the Basque Country (UPV/EHU), San Sebastian (Spain); Basque Foundation for Science, Bilbao (Spain). IKERBASQUE
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Energy Storage Research (JCESR); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1901908
- Alternate Identifier(s):
- OSTI ID: 1828475
- Grant/Contract Number:
- AC02-05CH11231; AC02-76SF00515; AC02- 05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Solid State Ionics
- Additional Journal Information:
- Journal Volume: 368; Journal ID: ISSN 0167-2738
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; Block copolymer electrolytes; Phase behavior; Hybrid organic-inorganic; Limiting current density; Concentrated solution theory; Ion transport
Citation Formats
Sethi, Gurmukh K., Frenck, Louise, Sawhney, Simar, Chakraborty, Saheli, Villaluenga, Irune, and Balsara, Nitash P. Effect of microphase separation on the limiting current density in hybrid organic-inorganic copolymer electrolytes. United States: N. p., 2021.
Web. doi:10.1016/j.ssi.2021.115702.
Sethi, Gurmukh K., Frenck, Louise, Sawhney, Simar, Chakraborty, Saheli, Villaluenga, Irune, & Balsara, Nitash P. Effect of microphase separation on the limiting current density in hybrid organic-inorganic copolymer electrolytes. United States. https://doi.org/10.1016/j.ssi.2021.115702
Sethi, Gurmukh K., Frenck, Louise, Sawhney, Simar, Chakraborty, Saheli, Villaluenga, Irune, and Balsara, Nitash P. Mon .
"Effect of microphase separation on the limiting current density in hybrid organic-inorganic copolymer electrolytes". United States. https://doi.org/10.1016/j.ssi.2021.115702. https://www.osti.gov/servlets/purl/1901908.
@article{osti_1901908,
title = {Effect of microphase separation on the limiting current density in hybrid organic-inorganic copolymer electrolytes},
author = {Sethi, Gurmukh K. and Frenck, Louise and Sawhney, Simar and Chakraborty, Saheli and Villaluenga, Irune and Balsara, Nitash P.},
abstractNote = {Hybrid organic-inorganic block copolymer electrolytes are of interest to enable batteries containing lithium metal anodes. The conductive block is a standard polymer electrolyte of poly(ethylene oxide) and the mechanically rigid block is an inorganic poly(acryloisobutyl polyhedral oligomeric silsesquioxane) polymer. Here, in this paper, we compare a poly(acryloisobutyl polyhedral oligomeric silsesquioxane)-b-poly(ethylene oxide)-b-poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (POSS-PEO-POSS) triblock copolymer and a poly(ethylene oxide)-b- poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (PEO-POSS) diblock copolymer mixed with lithium bis(trifluoromethanesulfonyl)imide salt. We have experimentally measured the limiting current density in lithium symmetric cells containing hybrid organic-inorganic electrolytes at 90 °C. The cells were polarized at a large range of applied current density. The diblock copolymer electrolyte exhibited a clear plateau in cell potential at all current densities below the limiting current density. At low applied current density, the triblock copolymer electrolyte also exhibited a clear plateau in cell potential. At currents approaching the limiting current density, the triblock copolymer electrolyte exhibited an underdamped potential profile. The cell potential did not reach a plateau at current densities above the limiting current in both systems. The diblock and triblock copolymer electrolytes were fully characterized using electrochemical methods to determine the ionic conductivity, cation current fraction, salt diffusion coefficient, and open circuit voltage as a function of salt concentration. Cell potential and salt concentration as functions of position in the cell at various current densities were calculated using Newman's concentrated solution theory. The theoretical limiting current density was calculated to be the current density at which salt is depleted at the cathode. We see quantitative agreement between experimental measurements and theoretical predictions for the limiting current density in the diblock copolymer electrolyte which has an ordered structure at all salt concentrations, while the experimental limiting current density is lower than the theoretical prediction for the triblock copolymer electrolyte, which exhibits a disordered morphology at high salt concentrations.},
doi = {10.1016/j.ssi.2021.115702},
journal = {Solid State Ionics},
number = ,
volume = 368,
place = {United States},
year = {Mon Jul 12 00:00:00 EDT 2021},
month = {Mon Jul 12 00:00:00 EDT 2021}
}
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