Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 161 (2016) 44–51

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Spectrochimica Acta Part A: Molecular and Biomolecular

Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Vibrational studies of flexible solid polymer electrolyte based on PCL–EC

incorporated with proton conducting NH4SCN
H.J. Woo ⁎, A.K. Arof
Centre for Ionics University of Malaya, Department of Physics, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: A flexible solid polymer electrolyte (SPE) system based on poly(ε-caprolactone) (PCL), a FDA approved non-toxic
Received 15 July 2015 and biodegradable material in the effort to lower environmental impact was prepared. Ammonium thiocyanate
Received in revised form 5 February 2016 (NH4SCN) and ethylene carbonate (EC) were incorporated as the source of charge carriers and plasticizing agent,
Accepted 28 February 2016
respectively. When 50 wt.% of ethylene carbonate (EC) was added to PCL–NH4SCN system, the conductivity
Available online 2 March 2016
increased by two orders from of 3.94 × 10−7 Scm−1 to 3.82 × 10−5 Scm−1. Molecular vibrational analysis via
Keywords:
infrared spectroscopy had been carried out to study the interaction between EC, PCL and NH4SCN. The
Vibrational studies relative percentage of free ions, ion pairs and ion aggregates was calculated quantitatively by deconvoluting
PCL the SCN− stretching mode (2030–2090 cm−1). This study provides fundamental insight on how EC influences
Coupling effect the free ion dissociation rate and ion mobility. The findings are also in good agreement to conductivity, differen-
Ion mobility tial scanning calorimetry and X-ray diffraction results. High dielectric constant value (89.8) of EC had made it an
Flexible polymer electrolyte effective ion dissociation agent to dissociate both ion pairs and ion aggregates, thus contributing to higher
number density of free ions. The incorporation of EC had made the polymer chains more flexible in expanding
amorphous domain. This will facilitate the coupling synergy between ionic motion and polymer segmental
motion. Possible new pathway through EC–NH+ 4 complex sites for ions to migrate with shorter distance has
been anticipated. This implies an easier ion migration route from one complex site to another.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction enables the polymer chain to exhibit segmental motion at room

Plasticizer was introduced to solid polymer electrolyte (SPE) as the
chain lubricant to enhance the ionic conductivity of solvent free SPEs
[1]. It has the ability to increase the amorphousness, lowering the
glass transition temperature, Tg and thus improve the ionic conductivity
[2–5] of the SPEs. When Tg is lower than room temperature, the polymer
is at the soft rubbery state. Polymer backbone becomes more flexible
and is thus expected to facilitate the coupling behaviour between
ionic motion and polymer segmental motion. The addition of high
dielectric constant polar solvent should also promote ion dissociation
and thus increasing the number density of free ions.
Woodruff and Hutmacher [6] have made a good review on
poly(ε-caprolactone) (PCL) describing why the research interest on
PCL increases drastically in the 21st century after being forgotten
for the last two decades. PCL is an aliphatic polyester that is non-
toxic as approved by Food and Drug Administration with tailorable
degradation kinetics [7–9]. In this work, PCL is used as the polymer
host for electrolytes because it contains a Lewis base (ester oxygen)
that can coordinate cations [10]. It also possesses low Tg, − 60 °C that
⁎ Corresponding author.
E-mail address: woohj@um.edu.my (H.J. Woo).
temperature.
From our previous work [11], the effect of ethylene carbonate (EC)
into PCL–NH4SCN complexes has been investigated via differential scan-
ning calorimetry (DSC), impedance spectroscopy and X-ray diffraction
(XRD) spectroscopy. Without addition of EC, the best proton conducting
SPEs exhibited ionic conductivity of 3.94 × 10−7 Scm−1. Conductivity
continued to increase monotonically with increasing EC content up to
3.82 × 10−5 Scm−1 at 50 wt.% EC. The incorporation of EC also showed
other observations such as reduction of Tg, appearance of new melting
peaks, Tm with lower melting temperature and decrease of the degree
of crystallinity. In this present work, molecular vibrational analysis via
infrared spectroscopy has been carried out to study the interaction be-
tween EC, PCL and NH4SCN. The functional carbonyl group, C_O in
the structure of PCL has lone pair of electrons in which the oxygen
atom is electronegative. It is therefore expected to act as the electron
donor and interact with the proton that is bonded covalently with the
nitrogen atom of ammonium salt. On the other hand, the ring structure
of EC also contains C_O which can allow complexation with the ammo-
nium salt. All the possible interactions will be studied by observing the
changes in position, intensity and shape of the IR spectra. IR analyses
shall provide fundamental insight on how EC influences the free ion
dissociation rate and ion mobility. The findings will be correlated to con-
ductivity, differential scanning calorimetry and X-ray diffraction results.

http://dx.doi.org/10.1016/j.saa.2016.02.034
1386-1425/© 2016 Elsevier B.V. All rights reserved.
 H.J. Woo, A.K. Arof / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 161 (2016) 44–51 45

2. Experimental section
2.1. Preparation of polymer electrolytes
PCL and EC (Aldrich) were used as received. NH4SCN (R&M
Marketing) were dried in an oven at 45 °C for 24 h prior to use. PE
consists of PCL, EC and NH4SCN were prepared by solution casting
technique. For interaction between PCL and EC, 10 wt.% and 30 wt.% of
EC were added to PCL. For interaction between EC and NH4SCN,
10 wt.% and 30 wt.% of ammonium salt were added to EC solution that
was heated to 40 °C. For interaction between PCL, NH4SCN and EC,
mixtures of PCL and NH4SCN were kept at PCL:NH4SCN weight ratio
74:26 and varying the EC content at (PCL–NH4SCN):EC weight ratio
from 0 wt.% to 50 wt.%.
All compositions were dissolved in 30 ml aprotic solvent tetrahydro-
furan (THF) with purity N99% from J.T. Baker. The mixtures were stirred
continuously with a magnetic stirrer for several hours at room temper-
ature until complete dissolution. The solutions were then cast into
different glass Petri dish and allow slow evaporation at 50 °C for 10 h.
The films were further dried slowly at room temperature inside a
desiccator for two weeks to remove any traces of solvent. The film's
thickness was ranging from 100 to 200 μm.
~ 2040 cm−1, ~2058 cm−1 and ~2074 cm−1 respectively. Thus, curve
fitting is applied to separate or deconvolute the envelope into individual
component bands. The relative percentage of free ions, ion pairs and ion
aggregates are estimated from the area under the respective band.
The experimental spectral envelope was first deconvoluted using
OMNIC software, by fixing the number and line shape while allowing
band parameters such as full width at half maximum (FWHM), area, in-
tensity and band shape to vary without constraints during the iteration.
All the deconvoluted spectra were best fitted using a constant baseline
and the Gaussian/Lorentzian function. The fitted spectral envelope
could then be reconstructed to check whether the fitting is good. Finally,
the individual fitted curve is analyzed according to the respective
vibrational modes.
3. Results and discussion
In order to study the interactions between PCL, EC and NH4SCN,
infrared analysis of PCL–EC, EC–NH4SCN and PCL–EC–NH4SCN systems
are studied. The assignments of IR spectra for PCL, EC and NH4SCN are
tabulated in Table 1.
3.1. Infrared studies of PCL–EC system

2.2. Instruments and methods
2.2.1. Attenuated total reflectance Fourier transform infrared (ATR-FTIR)
spectroscopy
ATR-FTIR spectroscopy was carried out on all polymer electrolyte
films using the Thermo Scientific Nicolet iSIO Smart ITR in the transmis-
sion mode over the wavenumber range from 4000 to 650 cm−1 at a
resolution of 1 cm−1.
2.2.2. Curve-fitting procedures
The intense peak of SCN− stretching mode is used to study the
effect of ion dissociation/reassociation in the present work. According
to the literature [12–14], this broad peak from 2030 to 2090 cm−1 is
composed of three narrower peaks. These peaks are the free anions
(SCN−), contact ion pairs (NH+ −
4 ·SCN ) and ion aggregates located at
A survey on literature on the interactions between polymer host and
plasticizers showed two different findings. Some researchers could not
observe interactions between the polymer host and plasticizer in PE
systems such as grafted natural rubber, MG30 and EC [15]. They ob-
served little or no difference in the IR spectra of the PEs upon addition
of EC. However, there were some literature reported that interactions
between polymer and plasticizer do occur. As an example, Wang et al.
[16] and Starkey [17] experimentally found that polymer–plasticizer
interactions occurred between the cyano (C`N) group of PAN with
the carbonyl (C_O) group of EC, PC and DMF.
In the present system, interaction between PCL and EC are investi-
gated by adding 10 wt.% and 30 wt.% of EC to the PCL films. Fig. 1
shows the FTIR spectra recorded at room temperature for pure EC,
pure PCL and PCL films added with 10 wt.% and 30 wt.% EC. As shown
in Fig. 1, PCL films added with 10 wt.% and 30 wt.% EC demonstrates

Table 1
Assignments of IR spectra for PCL, EC and NH4SCN.

Wavenumber (cm−1) Assignment Reference

PCL EC NH4SCN

3173 NH stretching [Awadhia and Agrawal, 2007]

2944 Asymmetric CH2 stretching [Wang et al., 2002]
2864 Symmetric CH2 stretching [Wang et al., 2002]
2052 Asymmetric C`N stretching [Zhang and Wang, 2009]
1784, 1766 Carbonyl, C_O stretching [Huang et al. 1996]
1736 Carbonyl, C_O stretching, amorphous phase [Chiu et al. 2004]
1720 Carbonyl, C_O stretching, crystalline phase [Chiu et al. 2004]
1619 Asymmetric C`N stretching [Zhang and Wang, 2009]
1552 CH2 scissoring [Masia et al., 2004]
1486, 1470 CH2 bending [Angell, 1956]
1419, 1389 CH2 wagging [Wang et al., 1996]
1415 NH deformation [Zhang and Wang, 2009]
1293 C–O and C–C stretching in the crystalline phase [Coleman and Zarian, 1979]
1239 Asymmetric COC stretching [Coleman and Zarian, 1979]
1230, 1216 CH2 twisting [Masia et al., 2004]
1190 OC–O stretching [Coleman and Zarian, 1979]
1170 Symmetric COC stretching [Kuo et al., 2001]
1157 C–O and C–C stretching in the amorphous phase [Kuo et al., 2001]
1139 Ring stretching [Masia et al., 2004]
1054 Ring breathing [Wang et al., 1996]
968 Skeletal stretching [Huang et al. 1996]
948 Symmetric SCN bending [Awadhia and Agrawal, 2007]
892 Ring breathing [Wang et al., 1996]
767 Ring stretching [Idris et al., 2007]
752 C–S stretching [Awadhia and Agrawal, 2007]
712 C_O bending [Huang et al. 1996]
46 H.J. Woo, A.K. Arof / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 161 (2016) 44–51
Fig. 1. Room temperature IR spectra of (a) pure EC, (b) pure PCL and PCL–EC films added
with (c) 10 wt.% and (d) 30 wt.% EC in the region between 650 and 2150 cm−1.
minimum or no difference in the IR spectra region from 650 to
1750 cm−1. However, a new peak appears at 1812 cm−1 upon addition
of 10 wt.% EC to PCL film. The intensity of this peak increases with
increasing EC content as presented in Fig. 2. This new peak could be
contributed from the C_O stretching of EC that is upshifted from
1784 cm−1, showing a dipole–dipole interaction between the PCL and
EC. Dipole–dipole interaction is the electrostatic interaction between
permanent dipoles in molecule. The partially electronegative-charge
oxygen atom of carbonyl group belonging to PCL can be attracted to
the partially electropositive-charge carbon atom of carbonyl belonging
to EC via electrostatic force [17].
3.2. Infrared studies of EC–NH4SCN system
The interactions between EC and NH4SCN are examined by adding
10 wt.% and 30 wt.% ammonium salt to EC electrolyte that was heated
to 40 °C. Fig. 3 exhibits the room temperature FTIR spectra of pure EC
and EC added with 10 wt.% and 30 wt.% NH4SCN.
Fig. 3 shows large wavenumber shifts in the IR spectra, indicating
interactions between the ammonium salt and EC. Upon incorpora-
tion of 10 wt.% NH4 SCN to EC, a clear peak at 2052 cm − 1 appears
due to the asymmetric C`N stretching of the salt. The intensity of
Fig. 2. Magnified IR spectra of (a) pure PCL, PCL–EC films added with (b) 10 wt.% and (c) 30 wt.% EC in the region between 1750 and 1850 cm−1.
Fig. 3. Room temperature IR spectra of (a) NH4SCN, (b) pure EC and EC–NH4SCN
electrolyte added with (c) 10 wt.% and (d) 30 wt.% NH4SCN.
this peak increases with increasing salt content as expected. Howev-
er, this cyano stretching mode at 1619 cm− 1 is observed to diminish
in EC electrolyte. In order to observe the wavenumber changes
clearly, the magnified IR spectra in the region from 1600 to
2000 cm− 1, 1200 to 1600 cm− 1 and 1190 to 690 cm− 1 are depicted
in Figs. 4, 5 and 6 respectively. The IR spectra with corresponding
wavenumber changes for EC added with 10 wt.% and 30 wt.%
NH4SCN is listed in Table 2.
As can be seen in Fig. 4, one of the two C_O stretching of EC at
1784 cm−1 upshifts to 1795 cm−1 (+Δ = 11 cm−1) but the other EC
carbonyl band at 1766 cm−1 is downshifted to 1760 cm−1. The relative
intensity of both carbonyl bands increase with increasing EC content.
According to Fini et al. [18], The C_O stretching mode of EC is split
into two bands due to Fermi resonance caused by dipole–dipole
coupling of two EC molecules.
CH2 modes of EC in Fig. 5 exhibit various responses with addition of
NH4SCN. The CH2 scissoring at 1552 cm−1 remains at the same position,
but with intensity reduction while the two CH2 bending modes original-
ly located at 1486 cm−1 and 1470 cm−1 merge to a single peak at
1474 cm−1. No significant changes of the CH2 wagging at 1419 cm−1
and 1389 cm−1 are observed. CH2 twisting bands at 1230 cm−1 and
1216 cm−1 merge into a shoulder at 1218 cm−1.
 H.J. Woo, A.K. Arof / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 161 (2016) 44–51
Fig. 4. Magnified IR spectra of (a) NH4SCN, (b) pure EC and EC–NH4SCN electrolyte added
with (c) 10 wt.% and (d) 30 wt.% NH4SCN in the region between 1600 and 1800 cm−1.
It is interesting to note that in Fig. 6, the ring stretching
of EC at 1139 cm− 1 shows a large position upshift to 1161 cm − 1
(+Δ = 22 cm − 1) while the same stretching mode at 767 cm − 1
upshift slightly to 771 cm−1. Both ring breathing bands at 1054 cm−1
and 892 cm− 1 shift to higher wavenumber at 1067 cm− 1 and
897 cm−1, respectively. Skeletal stretching mode is observed to upshift
marginally from 968 cm−1 to 971 cm−1 and finally the bending mode
of carbonyl move slightly from 712 cm− 1 to 717 cm−1. All the ring
stretching, ring breathing and skeletal stretching modes from the region
690 to 1190 cm−1 shift to higher wavenumber. This seems to show that
the interaction between EC and salt making the ring structure of EC
stiffer, thus requiring more energy for vibration.
3.3. Infrared studies of PCL–NH4SCN–EC system
Fig. 7 shows the IR spectra of PCL–NH4SCN–EC polymer electrolytes
in the region between 650 and 2250 cm− 1 whereby the interaction
between PCL, NH4SCN and EC will be investigated. These PE films con-
tain fixed amount of PCL and NH4SCN, 1.00 g and 0.35 g respectively,
but different concentrations of EC varying from 0 to 50 wt.%. The
magnified IR spectra in the region from 650 to 1150 cm−1 are depicted
in Fig. 8.
Fig. 5. Magnified IR spectra of (a) NH4SCN, (b) pure EC and EC–NH4SCN electrolyte added
with (c) 10 wt.% and (d) 30 wt.% NH4SCN in the region between 1200 and 1600 cm−1.
47
Fig. 6. Magnified IR spectra of (a) NH4SCN, (b) pure EC and EC–NH4SCN electrolyte added
with (c) 10 wt.% and (d) 30 wt.% NH4SCN in the region between 690 and 1190 cm−1.
All of the spectral changes within this region are similar to the
interactions between EC and NH4SCN, as elucidated in the earlier
section. The ring breathing bands upshift from 1054 cm− 1 and
892 cm−1 to 1068 cm−1 and 896 cm−1, respectively, skeletal stretching
mode upshifts from 968 cm− 1 to 971 cm− 1, ring stretching mode
upshifts from 767 cm− 1 to 771 cm− 1 and carbonyl bending mode
upshifts from 712 cm− 1 to 717 cm− 1. As such, PCL does not seem to
alter the interaction between EC and NH4SCN within this region.
The interactions between PCL, NH4SCN and EC in the region between
1500 and 1900 cm−1 would be interesting because both PCL and EC
contain carbonyl bond that may compete to interact with the NH+ 4 via
coordinate bond. Fig. 9 shows the IR spectra of PCL–NH4SCN–EC sys-
tems added with 0 to 50 wt.% EC in the region from 1500 to 1900 cm−1.
Upon addition of 10 wt.% EC to the PCL–NH4SCN system, the C_O
stretching band of PCL at 1720 cm−1 remain unshifted but shows a
rise in intensity. On the other hand, the peak at 1623 cm−1 is observed
to be very weak. From our previous work, evidence of interaction
between C_O of PCL and NH+ 4 upon addition of NH4SCN has been man-
ifested through the new peak appearance at 1623 cm−1. This suggests
that EC has weakened the interaction between PCL and NH4SCN.
In addition, two new peaks appear at 1773 cm−1 and 1807 cm−1.
The 1773 cm− 1 new peak could be attributed to the upshift of C_O
stretching band of EC from 1766 cm−1 as a result of interaction between
EC and NH4SCN of the PCL–NH4SCN system. The second new peak at
1807 cm− 1 could be due to the interaction between PCL and EC, an
upshift of the C_O stretching of EC from 1784 cm−1. This interaction
is also supported by our DSC studies (not included here) in which the
appearance of additional melting peak, Tm is attributed to the new
PCL–EC complex phases.
The weakening of PCL–NH4SCN interaction at 1623 cm−1 and the
strengthening of EC–NH4SCN interaction at 1773 cm−1 seems to show
that EC is a stronger competitor than PCL for interaction with NH+ 4 of
the ammonium salt. This shows that the addition of EC leads to the
formation of new EC–NH+ 4 complex which will reduce the fraction
of PCL–NH+ 4 complex. Therefore, a more flexible PCL chains with
less cross-linking is obtained, showing a reduced Tg value from DSC
studies [11]. Similar observation was made by Qian et al. (2002) in
PEO–LiClO4–EC system. A decrease of PEO–Li+ complex was reported
due to the formation of Li+–EC complex and lead to the lowering Tg.
As more EC is incorporated, the carbonyl stretching band of PCL remain
un-shifted at 1720 cm−1 and a new pair of doublet peaks at 1614 cm−1
and 1650 cm−1 is observed. The intensity of peaks at 1807 cm−1 and
1773 cm−1 keep increasing with increasing EC content. This indicates
a stronger interaction between EC and PCL and also between EC and
NH4SCN, respectively.
These polymer–plasticizer and ion–plasticizer interactions within
PCL–NH4SCN–EC system would interrupt polymer–polymer interaction
48 H.J. Woo, A.K. Arof / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 161 (2016) 44–51

Table 2
IR spectra with corresponding wavenumber changes for EC–NH4SCN electrolyte added with 10 wt.% and 30 wt.% NH4SCN.

Wavenumber (cm−1)
No. Assignments Remarks
Pure EC 10 wt.% NH4SCN 30 wt.% NH4SCN

1 C_O stretching 1784 1795 1795 Upshift 11 cm−1

2 C_O stretching 1766 1763 1760 Downshift 6 cm−1
3 CH2 scissoring 1552 1552 1552 Peak intensity reduces
4 CH2 bending 1486, 1470 1476 1474 2 peaks merge to single peak
5 CH2 wagging 1419 1419 1419 Peak intensity reduces
6 CH2 wagging 1389 1389 1389 Peak become broaden
7 CH2 twisting 1230, 1216 1218 1218 2 peaks merge to a shoulder
8 Ring stretching 1139 1158 1161 Upshift 22 cm−1
9 Ring breathing 1054 1066 1067 Upshift 13 cm−1
10 Skeletal stretching 968 971 971 Upshift 3 cm−1
11 Ring breathing 892 897 897 Upshift 5 cm−1
12 Ring stretching 767 770 771 Upshift 4 cm−1
C_O bending 712 716 717 Upshift 5 cm−1
13

either by occupying or increasing inter- and intra-chain separations
[19]. As a result, the crystalline domains are disrupted [20], explaining
the decrease of the relative degree of crystallinity, χC obtained from
XRD structural analysis [11]. When the amorphous region expands,
the polymer chains are more irregular and entangled, leading to a
loose molecular packing with smaller density. Hence, it is easier to
move the polymer chain in any plasticised PEs.
From the examination of IR spectra in the region between 1500 and
1900 cm−1, the alteration of peak intensity, appearance of new doublet
peaks and frequency shifts suggest that EC is interacting with both PCL
and NH4SCN and complexation has taken place in PCL–NH4SCN–EC sys-
tem. As such, the cation of the salt could interact with the carbonyl
group of both PCL and EC via coordinate bond as proposed in Fig. 10.
The addition of EC has possibly introduced new coordinating sites or
pathways for the cation to jump from one complex site to another
upon an applied electric field. The effective jump distance could get
shorten as depicted in Fig. 10. Therefore, it is in agreement with the
electrical studies where the activation energy for this PCL–NH4SCN–EC
system is found to be lower than the unplasticised PCL–NH4SCN system.
The transmittance spectra in the SCN− stretching mode between
2030 and 2090 cm−1 region are deconvoluted to study the effect of EC
in ion dissociation as presented in Fig. 11. The percentage of ionic
species is calculated based on the fraction of the integral area under
the curve, which is believed to be proportional to the relative concentra-
tion of ionic species. The results of individual fitted curve are displayed
in Fig. 12 as a function of EC concentration.
When low EC concentrations (10 and 20 wt.%) are added, a steady
increase of the integral area of free ions is observed from 36.0 to 38.2
and 41.9%, respectively. At the same time, the ion aggregates decrease
proportionally from 18.7 to 14.0 and 11.7%, respectively. The number
density of free ions seems to grow at the expense of ion aggregates.
On the other hand, the fraction of contact ion pair at 10 wt.% EC
rises slightly from 45.3 to 47.8% but at 20 wt.% drops back marginally
to 46.4%.
Upon further incorporation of EC to 30 wt.%, the integral area
percentage of free ions enhance dramatically to 58.7%. The integral
area fraction of ion aggregate drops to 0% reflecting the absence of
bigger size ion aggregates that do not contribute to conductivity in the
sample. At the same time, percentage of contact ion pair decreases
gradually to 41.3%. For the first time, the percentage of free ions
overtakes that of contact ion pairs.
At high EC concentrations (40 and 50 wt.%), the number of free ions
continue to increase consistently to 70.4% and 73.5%, respectively.
However, the contact ion pairs are found to drop to 29.6% and 26.5%,

Fig. 7. Evolution of room temperature IR spectra of (a) NH4SCN, (b) pure EC, (c) pure PCL Fig. 8. Magnified IR spectra of PCL–NH4SCN–EC films added with 0 to 50 wt.% EC in the
and PCL–NH4SCN–EC films added with 0 to 50 wt.% EC. region between 650 and 1150 cm−1.
 H.J. Woo, A.K. Arof / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 161 (2016) 44–51 49

Fig. 9. Magnified IR spectra of PCL–NH4SCN–EC films added with 0 to 50 wt.% EC in the region between 1500 and 1900 cm−1.

Fig. 10. Schematic representation of the cation coordination in PCL–NH4SCN–EC polymer complex. The dotted line represents the ion–dipole interaction between cation and PCL and stripe
line represents the dipole–dipole interaction between PCL and EC. Arrow shows the direction of the cation movement.
50 H.J. Woo, A.K. Arof / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 161 (2016) 44–51
Fig. 11. The curve-fitting IR spectra of PCL–NH4SCN–EC films added with 0 and 40 wt.% EC
displaying CN stretching modes. Open circles represent the experimental data and red
dotted line depicts the cumulative fit for all individual spectra.
respectively. This result could be understood from the high dielectric
constant value (89.8) of cyclic EC. With high dielectric constant, EC
has high dissociation ability to prevent ion-pair formation or high effec-
tiveness on shielding the interionic coulomb attraction between cations
and anions. According to Bjerrum [21], the critical distance, r for ion pair
formation is reciprocal to the dielectric constant, ε' value as shown in
the following equation:
r. Thus, in a system with high ε' value, it is more difficult for cations
and anions to be close enough to fulfill the criteria (smaller than r) for
ion pair formation to take place.
Following the above discussion, in a polymer system incorporated
with high ε' material like EC, ion association is unlikely to happen and
most ions would stay free. Thus, EC is also acting as an additive to pro-
mote ion dissociation. Although EC is intended to be used as plasticizing
solvent to enhance the conductivity by reducing Tg and degree of
crystallinity, it is found that EC can also increase number density of
free ions in the polymer electrolyte system.
These results are in agreement with other reported literature
[22–24]. In PEO–LiCF3SO3–EC system of Chintapalli and Frech [23],
their FTIR results showed that addition of EC increases the number
of free ions drastically. Kumar and Sekhon [24] found the same con-
clusion in PEO–NH4 F–DMA system, Forsyth and co-workers [22]
used NMR spectroscopy in PEG–NaCF3SO3–PC system to conclude
that PC significantly increased the number of free sodium ions.
Therefore, these deconvolution results clearly suggest that the addi-
tion of EC into PCL–NH4SCN system helps to dissociate ion pairs and
higher aggregates, leading to a higher number of free ions.
4. Conclusions
Vibrational studies of flexible solid polymer electrolyte based on
PCL–NH4SCN–EC system has been investigated. The room tempera-
ture conductivity of the SPE has increased from 3.94 × 10− 7 Scm− 1
(without EC) to 3.82 × 10−5 Scm−1 at 50 wt.% EC. This improvement
was contributed by the increase in number density of ions and ion mo-
bility. The relative percentage of free ions, ion pairs and ion aggregates
was calculated quantitatively by deconvoluting the SCN− stretching
mode (2030–2090 cm−1). The number density of free ions was proven
to increase with increasing EC content. The high dielectric constant
value (89.8) of EC had made EC an effective ion dissociation agent. Ion
pairs and aggregates were dissociated contributing to more free ions.
On the other hand, the enhancement of ion mobility in this flexible
SPE membrane could be anticipated by looking at the interaction
between PCL, NH4SCN and EC. Interactions have been demonstrated
through appearance of new shoulder, changes in peak intensities and
peak position. The incorporation of EC had made the polymer chains
more flexible in expanding amorphous domain. This will facilitate
  the coupling behaviour between ionic motion and polymer segmental
zi z j e2
r¼ ð1Þ
8πε0 ε0 kT
Here, z is the valency of the cations and anions, e is the elementary
electron charge, ε0 is the dielectric constant in vacuum, k is Boltzmann's
constant (= 8.6173 × 10− 5 eV K−1) and T is temperature. Ion pair
formation is likely to occur when the distance between cation and
anion is smaller than r. According to Eq. (1), high ε' value means small
Fig. 12. Integral area percentage of free ions, contact ion pairs and ion aggregates as a
function of EC concentration for PCL–NH4SCN–EC system.
−1
motion. The new EC–NH+ 4 complex sites at 1773 cm may possibly
act as new pathways for ions to migrate with shorter distance. This
implies easier ion migration or higher ion mobility from one complex
site to another.
Acknowledgement
This research was funded by University of Malaya (RG324-15AFR)
and the Ministry of Education of Malaysia (FP053-2014A).
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