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Title: Effect of microphase separation on the limiting current density in hybrid organic-inorganic copolymer electrolytes

Journal Article · · Solid State Ionics
 [1];  [2];  [3];  [4];  [5];  [6]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  3. Univ. of California, Berkeley, CA (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division
  5. Univ. of the Basque Country (UPV/EHU), San Sebastian (Spain); Basque Foundation for Science, Bilbao (Spain). IKERBASQUE
  6. 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
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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.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
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)
Grant/Contract Number:
AC02-05CH11231; AC02-76SF00515; AC02- 05CH11231
OSTI ID:
1901908
Alternate ID(s):
OSTI ID: 1828475
Journal Information:
Solid State Ionics, Vol. 368; ISSN 0167-2738
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

References (33)

Phase Behavior of Mixtures of Block Copolymers and a Lithium Salt journal August 2018
Nika : software for two-dimensional data reduction journal March 2012
Noise Phenomena in Electrochemical Impedance Spectroscopy of Polymer Electrolyte Membrane Electrolysis Cells journal July 2018
The determination of transference numbers in solid polymer electrolytes using the Hittorf method journal July 1992
The Measurement of a Complete Set of Transport Properties for a Concentrated Solid Polymer Electrolyte Solution journal January 1995
Correlating Microstructural Lithium Metal Growth with Electrolyte Salt Depletion in Lithium Batteries Using 7 Li MRI journal November 2015
Limiting currents in the polymer electrolyte: PEOxLiCF3SO3 journal December 1983
Anomalous Self-Assembly and Ion Transport in Nanostructured Organic–Inorganic Solid Electrolytes journal August 2018
Determination of Transport Parameters in Liquid Binary Lithium Ion Battery Electrolytes: I. Diffusion Coefficient journal January 2017
Excellent Cycle Life of Lithium-Metal Anodes in Lithium-Ion Batteries with Mussel-Inspired Polydopamine-Coated Separators journal April 2012
Potentiometric measurements of ionic transport parameters in poly(ethylene oxide)-LiX electrolytes journal May 1987
Structure and Thermodynamics of Hybrid Organic–Inorganic Diblock Copolymers with Salt journal April 2019
Comparing Measurements of Limiting Current of Electrolytes with Theoretical Predictions up to the Solubility Limit journal September 2019
Comparing Cycling Characteristics of Symmetric Lithium-Polymer-Lithium Cells with Theoretical Predictions journal January 2018
A novel polyhedral oligomeric silsesquioxane based ionic liquids (POSS-ILs) polymer electrolytes for lithium ion batteries journal June 2018
Effect of crystallization of the polyhedral oligomeric silsesquioxane block on self-assembly in hybrid organic-inorganic block copolymers with salt journal June 2021
Effect of salt concentration profiles on protrusion growth in lithium-polymer‑lithium cells journal December 2020
Three-dimensional analysis of transport and electrochemical reactions in polymer electrolyte fuel cells journal January 2004
A novel room temperature POSS ionic liquid-based solid polymer electrolyte journal February 2018
Building better batteries journal February 2008
Factors That Control the Formation of Dendrites and Other Morphologies on Lithium Metal Anodes journal November 2019
Comparing Experimental Measurements of Limiting Current in Polymer Electrolytes with Theoretical Predictions journal January 2019
Li-ion hopping conduction in highly concentrated lithium bis(fluorosulfonyl)amide/dinitrile liquid electrolytes journal January 2019
Transport Properties of the Solid Polymer Electrolyte System P(EO) n LiTFSI journal April 2000
Relationship between Segmental Dynamics Measured by Quasi-Elastic Neutron Scattering and Conductivity in Polymer Electrolytes journal March 2018
A study of electrochemical kinetics of lithium ion in organic electrolytes journal July 2002
Lithium Metal Anodes: Toward an Improved Understanding of Coupled Morphological, Electrochemical, and Mechanical Behavior journal February 2017
Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies journal January 2020
Effect of Molecular Weight and Salt Concentration on Conductivity of Block Copolymer Electrolytes journal July 2009
Mapping of Lithium-Ion Battery Electrolyte Transport Properties and Limiting Currents with In Situ MRI journal October 2020
Characterisation and modelling of the transport properties in lithium battery polymer electrolytes journal November 2001
Beyond PEO—Alternative host materials for Li + -conducting solid polymer electrolytes journal June 2018
Limiting current density in bis(trifluoromethylsulfonyl)amide-based ionic liquid for lithium batteries journal February 2011

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Related Subjects

25 ENERGY STORAGE
Block copolymer electrolytes
Phase behavior
Hybrid organic-inorganic
Limiting current density
Concentrated solution theory
Ion transport