Glass transition and free volume behaviour of poly(acrylonitrile)/LiCF3SO3 polymer-in-salt electrolytes compared to poly(ether urethane)/LiClO4 solid polymer electrolytes

Forsyth, M., MacFarlane, D. R. and Hill, A. J. 2000, Glass transition and free volume behaviour of poly(acrylonitrile)/LiCF3SO3 polymer-in-salt electrolytes compared to poly(ether urethane)/LiClO4 solid polymer electrolytes, Electrochimica acta, vol. 45, no. 8-9, pp. 1243-1247.

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Title Glass transition and free volume behaviour of poly(acrylonitrile)/LiCF3SO3 polymer-in-salt electrolytes compared to poly(ether urethane)/LiClO4 solid polymer electrolytes
Formatted title Glass transition and free volume behaviour of poly(acrylonitrile)/LiCF3SO3 polymer-in-salt electrolytes compared to poly(ether urethane)/LiClO4 solid polymer electrolytes
Author(s) Forsyth, M.
MacFarlane, D. R.
Hill, A. J.
Journal name Electrochimica acta
Volume number 45
Issue number 8-9
Start page 1243
End page 1247
Publisher Elsevier Science Pub. Co.
Place of publication New York, N.Y.
Publication date 2000-01-03
ISSN 0013-4686
1873-3859
Keyword(s) polymer-in-salt electrolytes
positron annihilation lifetime spectroscopy
glass transition
poly(acrylonitrile)
LiCF3SO3
Summary Measurements of the glass transition temperature (Tg) and free volume behaviour of poly(acrylonitrile) (PAN) and PAN/lithium triflate (LiTf), with varying salt composition from 10 to 66 wt% LiTf, were made by positron annihilation lifetime spectroscopy (PALS). Addition of salt from 10 to 45 wt% LiTf resulted in an increase in the mean free volume cavity size at room temperature (r.t.) as measured by the orthoPositronium (oPs) pickoff lifetime, τ3, with little change in relative concentration of free volume sites as measured by oPs pickoff intensity, I3. The region from 45 to 66 wt% salt displayed no variation in relative free volume cavity size and concentration. This salt concentration range (45 wt%<[LiTf]<66 wt%) corresponds to a region of high ionic conductivity of order 10−5 to 10−6 S cm−1 at Tg as measured by PALS. A percolation phenomenon is postulated to describe conduction in this composition region. Salt addition was shown to lower the Tg as measured by PALS; Tg was 115°C for PAN and 85°C for PAN/66 wt% LiTf. The Tg and free volume behaviour of this polymer-in-salt electrolyte (PISE) was compared to a poly(ether urethane)/LiClO4 where the polymer is the major component, i.e. traditional solid polymer electrolyte (SPE). In contrast to the PISE, the Tg of the SPE was shown to increase with increasing salt concentration from 5.3 to 15.9 wt%. The relative free volume cavity size and concentration at r.t. were shown to decrease with increasing salt concentration. Ionic conductivity in this SPE was of order 10−5 S cm−1 at r.t., which is over 60°C above Tg, 10−8 S cm−1 at 25°C above Tg, and conductivity was not measurable at Tg.
Language eng
Field of Research 039999 Chemical Sciences not elsewhere classified
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1.1 Refereed article in a scholarly journal
Copyright notice ©2000, Elsevier Science Ltd.
Persistent URL http://hdl.handle.net/10536/DRO/DU:30030131

Document type: Journal Article
Collection: Institute for Technology Research and Innovation
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