Relaxation Dynamics and Ion Conduction of Poly(Ethylene Carbonate/Ethylene Oxide) Copolymer-Based Electrolytes

Doi, Yuya; Allgaier, Jürgen; Zorn, Reiner; Förster, Stephan; Egami, Takeshi; Ohl, Michael

doi:10.1021/acs.jpcc.2c06941

Relaxation Dynamics and Ion Conduction of Poly(Ethylene Carbonate/Ethylene Oxide) Copolymer-Based Electrolytes

Journal Article · Tue Nov 29 00:00:00 EST 2022 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.2c06941· OSTI ID:1906617

^[1]; ^[2]; ^[2]; ^[2]; ^[3]; Ohl, Michael ^[2]

Jülich Centre for Neutron Science (JCNS) (Germany); Nagoya University (Japan)
Jülich Centre for Neutron Science (JCNS) (Germany)
University of Tennessee, Knoxville, TN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Poly(ethylene carbonate/ethylene oxide) P(EC/EO) copolymer was synthesized from EC monomer as a new matrix component of solid polymer electrolytes (SPEs), and the correlation between polymer dynamics and ionic conductivity in the P(EC/EO)-based SPEs at various lithium salt weight fractions (w_Li) was investigated by dielectric spectroscopy, rheology, and molecular dynamics (MD) simulations. With the addition of lithium salt, the molecular motions at various scales (i.e., from local to segmental and global motion scales) were found to change as follows: (i) the local motion of P(EC/EO) was slightly accelerated, and at w_Li≥ 0.22, it was separated into two relaxation modes, one faster and the other slower than that of P(EC/EO), (ii) the segmental motion of P(EC/EO) became significantly slower with the addition of lithium salt, and (iii) the global terminal relaxation became slightly slower with the increase of w_Li. Thus, the motion of P(EC/EO) at various scales in SPEs changed with different trends with increasing lithium salt. It was also found that the temperature dependence of the ionic conductivity was described by a Vogel–Fulcher–Tammann-type function, which was correlated with the segmental motion, as is known in other SPE systems. Furthermore, from MD simulations, lithium ions are coordinated with the EC units more likely and with a closer distance than EO units in P(EC/EO), and the coordination number of oxygens around one lithium ion was estimated as 6–7 at the distance of 0.30 nm. Here, these results suggest that the coordination structure of the oxygens around the lithium ion is slightly disrupted due to the presence of EC units compared to the chelating structure of pure PEO electrolytes.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1906617

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 48 Vol. 126; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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