Investigation of Ionic Conduction in PEO-PVDF Base-3

JOURNAL OF APPLIED PHYSICS 123, 125102 (2018)
Investigation of ionic conduction in PEO–PVDF based blend polymer

electrolytes
Subir Kumar Patla,1,2 Ruma Ray,1 K. Asokan,3 and Sanat Karmakar2,a)
1
Physics Department, Gurudas College, Kolkata 700054, India
2
Soft Matter and Biophysics Laboratory, Department of Physics, Jadavpur University, Kolkata 700032, India
3
Inter University Accelerator Centre, New Delhi 110067, India
(Received 10 January 2018; accepted 7 March 2018; published online 26 March 2018)
We investigate the effect of blend host polymer on solid polymer electrolyte (SPE) films doped
with ammonium iodide (NH4I) salt using a variety of experimental techniques. Structural studies
on the composite SPEs show that the blending of Poly(ethylene oxide) (PEO)–Poly(vinylidene
fluoride) (PVDF) polymers in a suitable ratio enhances the amorphous fraction of the polymer
matrix and facilitates fast ion conduction through it. We observe that the addition of a small
amount of PVDF in the PEO host polymer enhances the ion – polymer interaction leading to more
ion dissociation. As a result, the effective number of mobile charge carriers within the polymer
matrix increases. Systematic investigation in these blend SPEs shows that the maximum
conductivity (1.01 10–3 S/cm) is obtained for PEO – rich (80 wt. % PEO, 20 wt. % PVDF)
composites at 35 wt. % NH4I concentration at room temperature. Interestingly, at higher salt
concentrations (above 35 wt. %), the conductivity is found to decrease in this system. The
reduction of conductivity at higher salt concentrations is the consequence of decrease in the carrier
concentration due to the formation of an ion pair and ion aggregates. PVDF–rich compositions
(20 wt. % PEO and 80 wt. % PVDF), on the other hand, show a very complex porous
microstructure. We also observe a much lower ionic conductivity (maximum 10–6 S/cm at 15 wt.
% salt) in these composite systems relative to PEO-rich composites. Published by AIP Publishing.
https://doi.org/10.1063/1.5022050
I. INTRODUCTION PEO and PVDF polymers have been confirmed26 earlier. The
choice of PVDF is based on its compatibility to form the
Solid polymer electrolytes (SPEs) have drawn tremen-
blend with PEO27,28 with good thermal stability.29–31 Most of
dous attention for various electrochemical applications. The
the studies reported earlier have used Li salts to achieve maxi-
advantages of solid electrolytes include primarily their easy
mum conductivity. The lower lattice energy of SPEs in the
preparation techniques, dimensionality, flexibility, good elec-
presence of ammonium iodide (NH4I), compared to other
trochemical stability, safety, and durability. However, the
alkali metal salts, motivates us to study this system.32
main limitation of SPE is associated with its poor conductivity
In case of NH4I, the ion–polymer complexation occurs
at ambient temperature. Numerous research groups are putting
between the ether oxygen of the PEO chain and the ammo-
intensive efforts to achieve improved conductivity at room
nium ion (O: NH4þ) through hydrogen bonding.33 The coor-
temperature by different ways, like crosslinking of molecules
dination influences the local structure of the polymer matrix.
by means of chemical additives, high energy perturbations,1,2
The strengths of four hydrogen bonds within the tetrahedral
synthesizing or identifying more amorphous polymer hosts,3–5
by adding a suitable plasticizer to enhance polymer flexibil- NH4þ ion forming the N–H ….I bond, are different. Out of
ity,6–8 trapping of a liquid organic material to produce hybrid these four bonds, the weakest bond can be easily dissociated
polymer electrolytes,9–11 using suitable co–polymer, blending producing a mobile Hþ ion, hopping through the amorphous
of two polymers,12–14 and so on. Polymer blending is a viable part of the polymer matrix via coordinating sites (ether oxy-
technique in this context15 depending on the properties of gen). Actually, this polymer composite is a protonic conduc-
component polymers and their mixing conditions.16,17 Similar tor. Ion dissociation and hopping of charged species usually
experiments on various polymer electrolytes, in the form of a takes place in amorphous regions due to reduced energy bar-
solid or as a gel, with various blend combinations show con- riers31 and thus except special circumstances, crystalline
ductivity enhancement.16–25 regions do not contribute to ion conduction. (See Fig. 1S in
The effect of blending, as compared to an individual host the supplementary material.)
polymer Poly(ethylene oxide) (PEO) and Poly(vinylidene Polymer blending is expected to incorporate new ion–
fluoride) (PVDF) and the influence of salt on the structure and coordinating sites and the local crystallinity is disturbed
morphology of PEO-PVDF blend composites have been depending on the properties of the constituent polymers and
extensively investigated. The complexation and miscibility of their mixing conditions.16,17 The present study aims to
develop Solid Polymer Electrolytes (SPEs) utilizing
a)
Author to whom correspondence should be addressed: sanatkarmakar@ PEO–PVDF blend hosts for improved ionic conductivity at
gmail.com room temperature.
0021-8979/2018/123(12)/125102/11/$30.00 123, 125102-1 Published by AIP Publishing.

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JOURNAL OF APPLIED PHYSICS 123, 125102 (2018)

Investigation of ionic conduction in PEO–PVDF based blend polymer

0021-8979/2018/123(12)/125102/11/$30.00 123, 125102-1 Published by AIP Publishing.

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