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Conductivity, XRD, and FTIR studies of new Mg2+-ion-conducting solid

polymer electrolytes: [PEG: Mg(CH3COO)2]

Article  in  Journal- Korean Physical Society · August 2011

DOI: 10.3938/jkps.59.114

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Journal of the Korean Physical Society, Vol. 59, No. 1, July 2011, pp. 114∼118

Conductivity, XRD, and FTIR Studies of New Mg2+ -ion-conducting Solid

Polymer Electrolytes: [PEG: Mg(CH3 COO)2 ]

Anji Reddy Polu and Ranveer Kumar∗

Department of Physics, Dr. Hari Singh Gour University, Sagar 470003, India

Valerio Causin and Ramesh Neppalli

Department of Chemical Sciences, University of Padova, Padova 35131, Italy

(Received 7 April 2011, in final form 16 May 2011)

Solid polymer electrolytes based on poly (ethylene glycol) (PEG) doped with Mg(CH3 COO)2 have
been prepared by using the solution–casting method. The X-ray diffraction patterns of PEG with
Mg(CH3 COO)2 salt indicated a decrease in the degree of crystallinity with increasing concentration
of the salt. The complexation of Mg(CH3 COO)2 salt with the polymer was confirmed by using
Fourier transform infrared spectroscopy (FTIR) studies. The ionic conductivity was measured for
the [PEG: Mg(CH3 COO)2 ] system in the frequency range 50 Hz - 1 MHz. The addition of Mg
salt was found to improve the ionic conductivity significantly. The 15-wt-% Mg(CH3 COO)2 -doped
system had a maximum conductivity of 1.07 × 10−6 S/cm at 303 K. The conductance spectrum
shows two distinct regions: a dc plateau and a dispersive region. The temperature dependence of the
ionic conductivity reveals the conduction mechanism to be an Arrhenius-type thermally activated
process.

PACS numbers: 81.05.Lg, 82.45.Gj, 82.47.-a

Keywords: PEG, Ionic conductivity, XRD, Polymer electrolyte, Mg(CH3 COO)2
DOI: 10.3938/jkps.59.114

I. INTRODUCTION
The pioneering work in the field of solid polymer
electrolytes (SPEs) was carried out by Wright and co-
workers [1,2], who reported ionic conductivities of the
order of 10−5 S/cm at 330 K in highly crystalline PEO-
NaSCN complexes. Since then considerable progress has
been made in this field [3]. In the past few decades,
SPEs have gained considerable attention due to their in-
teresting and wide application potentials in high-energy-
density batteries, sensors and fuel cells [4,5].
SPEs based on Mg2+ -ion-conducting salts have at-
tracted considerable attention in the recent years as
promising candidates for fabricating all-solid-state elec-
trochemical power sources. The present day scenario in
the field of battery technology is that most of the com-
mercially available solid state rechargeable batteries are
based on Li/Li+ -ion SPEs. Li metal, but Li+ -salts suf-
fer from several operational limitations, viz. difficulty in
handling in open ambience due to highly reactive materi-
als, high cost, etc. Thus, solid state rechargeable batter-
ies based on Mg/Mg2+ -ion salt SPEs look very attractive
as they are expected to give battery performance capa-
bilities close to those of Li/Li+ -ion SPE batteries due
∗ E-mail: ranveerssi@yahoo.com
-114-
to the fact that Mg2+ -ions have ionic size and weight
comparable to those of Li+ -ions.
In recent years, several different strategies have been
employed to enhance the ionic conductivity and the
cation transport number. To date, poly (ethylene oxide)
(PEO)- and poly (ethylene glycol) (PEG)-based polymer
electrolytes have been regarded as some of the most suit-
able electrolytes for rechargeable batteries. Most studies
on the concentration and the temperature dependences
and on conductivity enhancement have been on high-
molecular-weight polymers (e.g., PEO) complexed with
alkali metal salts (lithium being the most studied) [6–
10]. However, not much attention has been paid to the
somewhat low-molecular-weight (MW ∼ 4000) PEOs or
PEGs. PEG has the same monomeric unit as PEO, but
has an end hydroxyl group, with the chemical formula
H (-CH2-CH2-O-)n -OH. The PEG (MW = 4000) used
in our studies is a solid at room temperature, having a
melting point close to 60 ◦ C.
In the present work, Mg2+ -ion-conducting polymer
electrolytes based on poly (ethylene glycol) complexed
with Mg(CH3 COO)2 were prepared by using a solution
casting technique. The polymer electrolytes were charac-
terized by using X-ray diffraction (XRD), Fourier trans-
form infrared (FTIR) and complex impedance spectro-
scopic analyses.
Conductivity, XRD, and FTIR Studies of New Mg2+ -ion-conducting Solid · · · – Anji Reddy Polu et al. -115-

II. EXPERIMENTAL DESCRIPTION

1. Sample Preparation

PEG (average molecular weight 4,000) purchased from

CDH, India, was dried at 40 ◦ C for 5 h; Mg(CH3 COO)2
(CDH, India) was dried at 40 ◦ C for 24 h. Solid poly-
mer electrolyte samples were prepared using the solution-
casting technique. PEG (molecular weight 4,000) was
used as the polymer. Mg(CH3 COO)2 was added ap-
propriately. The solvent used in this work was distilled
water. The mixture was stirred for up to 10 hours to
obtain a homogeneous solution. The solution was then
poured into glass petri dishes and evaporated slowly at
room temperature under vacuum. The polymer elec-
trolyte samples were then transferred into a desiccator
for further drying before the test.

2. XRD and IR

The XRD patterns for the PEG-based polymer elec-

trolyte samples were recorded using a Philips XPERT
diffractometer at a scan rate of 0.02◦ per min. Infrared
spectra profiles were obtained using a SHIMADZU-8000
Fourier transform infrared (FTIR) spectrophotometer in
the range 400 - 4,000 cm−1 in the transmittance mode
at room temperature.

3. Impedance Spectroscopy Fig. 1. (Color online) X-ray diffraction patterns of (a)

Impedance measurements were carried out using a
HIOKI 3532-50 impedance analyzer in the frequency
range from 50 Hz to 1 MHz with a specially-designed
spring press that was fitted with stainless-steel electrodes
and exerted a small pressure on the sample to ensure
good contact. The samples were pressed into pellets us-
ing Teflon moulds.
III. RESULTS AND DISCUSSION
1. XRD and IR
Figure 1(a) shows the XRD patterns for pure PEG and
for various salt compositions of the polymer-salt com-
plexes. Figure 1(b) shows the XRD pattern for pure Mg
acetate salt. A comparison of the X-ray diffraction pat-
terns of PEG:Mg(CH3 COO)2 salt with that of pure PEG
shows that the diffraction peaks between 2θ = 19.2◦ and
23.4◦ are less intense in the Mg(CH3 COO)2 complexed
films. This indicates a decrease in the degree of crys-
tallinity of the PEG with increasing concentration of the
PEG: x wt % of Mg(CH3 COO)2 (x = 0, 5, 10, 15, 20, and
25) and (b) pure Mg(CH3 COO)2 .
salt. The peaks corresponding to the polymer still ap-
pears in the XRD pattern of SPEs while the peaks corre-
sponding to Mg(CH3 COO)2 (peaks at 2θ = 20.8◦ , 27.7◦ ,
30.7◦ , and 32.3◦ ) in the XRD plots of SPEs disappear.
This confirms the complexation between the host poly-
mer and the salt.
The FTIR spectra of PEG, Mg(CH3 COO)2 and PEG:
Mg(CH3 COO)2 materials are shown in Fig. 2. Polyethy-
lene glycol exhibits absorptions of a primary alcohol.
Hence, these absorptions, which are comprised of stretch-
ing and bending vibrations, are restricted to C-C stretch-
ing, C-O stretching, C-H stretching (methylene absorp-
tions) and C-H bending. The methylene group found in
PEG has been found to vibrate in the stretching mode
around 2875 cm−1 . The absorption around 1465 cm−1
is due to binding vibration of -CH2 . As in the case of a
primary alcohol, the C-O stretching vibration, a strong
bond around 1280 cm−1 is also observed. A sharp, strong
bond at 947 cm−1 and 842 cm−1 is due to the C-C
stretching. Addition of Mg(CH3 COO)2 produces neither
a change in the nature of PEG itself structurally nor a
-116-
Fig. 2. (Color online) FTIR spectra for (a) PEG, (b)
Mg(CH3 COO)2 , and (c) 85PEG: 15Mg(CH3 COO)2 .
break up of the chain.
The group frequencies at 2740.94, 2694.65, 1359.86,
1342.5, 1280.78, 1242.2, 1145.75, 1111.03, 1060.88,
962.51, and 842.92 cm−1 of PEG and 1558.54, 1541.18,
1521.89, and 949.01 cm−1 of Mg(CH3 COO)2 are found in
Journal of the Korean Physical Society, Vol. 59, No. 1, July 2011
Fig. 3. (Color online) Impedance plot for the highest con-
ductivity polymer electrolyte [85PEG: 15Mg(CH3 COO)2 ] at
different temperatures.
the complex as are some new peaks at 3524.06, 3122.86,
1417.73, 669.32, 659.68 cm−1 . The above analysis estab-
lishes the formation of the polymer-salt complex.
2. Impedance Analysis
Impedance spectroscopy is a relatively new and pow-
erful method for characterizing many of the electrical
properties of electrolyte materials and their interfaces
with electronically conducting electrodes. An Impedance
plot (plot between the real and the imaginary parts of
impedance) for 85PEG:15Mg(CH3 COO)2 polymer com-
plex at different temperatures is shown in Fig. 3. The
plots consist of a high-frequency broadened semicircle
due to a frequency-dependent capacitor (Cg ) parallel to
the bulk resistor. The point where the semicircle in-
tersects the real axis gives the value of the bulk resis-
tance (Rb ). It can be observed from the plots that as
the temperature increases, the diameter of the semicir-
cle at higher frequency decreases, implying that the bulk
resistance (Rb ) decreases. By knowing the bulk resis-
tance (Rb ) along with the dimensions of the sample, one
can calculate the conductivity of the sample by using the
relation
σ = L/Rb A, (1)
where L and A are the thickness and the area of the
polymer electrolyte samples, respectively.
3. Conductivity Analysis
The ionic conductivity of polymer electrolytes as a
function of magnesium acetate concentration at room
Conductivity, XRD, and FTIR Studies of New Mg2+ -ion-conducting Solid · · · – Anji Reddy Polu et al.
Table 1. Transport parameters of the PEG -
Mg(CH3 COO)2 polymer electrolyte at 303 K.
Conductivity σb σdc from conductance spectra
Sample
at 303 K (S/cm) (S/cm) at 303 K
100:0 5.41E-08 5.32E08
95:05 4.23E-07 4.21E-07
90:10 3.33E-07 3.34E-07
85:15 1.07E-06 1.06E-06
80:20 8.36E-07 8.11E-07
75:25 9.21E-07 9.43E-07
Fig. 4. (Color online) Effect of the concentration of mag-
nesium acetate on the conductivity of poly(ethylene glycol)
at room temperature (303 K).
temperature (303K) is presented in Fig. 4. The
ionic conductivity of different compositions of PEG-
Mg(CH3 COO)2 complexes are given in Table 1. Pure
PEG 4000 shows a low ionic conductivity (∼5.41 × 10−8
S/cm) at room temperature (303 K). With the addition
of 15 wt% of Mg(CH3 COO)2 salt, the ionic conductivity
is enhanced to 1.07 × 10−6 S/cm.
Jeon et al. [11] reported that the conductivity of poly-
mer electrolytes increased with increasing salt concentra-
tion, but further addition of the salt caused the conduc-
tivity to decrease. MacCallum et al. [12] explained that
the conductivity increases initially with increasing salt
concentration as the number of charge carriers increases,
but at higher salt concentrations, the conductivity de-
creases because of the increasing influence of ion pairs,
ion triplets, and higher ion aggregations, which reduces
the overall mobility and the number of effective charge
carriers.
The logarithmic conductivity as a function of fre-
quency for PEG:Mg(CH3 COO)2 electrolytes with dif-
ferent compositions at 303 K and the 85PEG:15Mg
(CH3 COO)2 polymer complex at different temperatures
are shown in Figs. 5(a) and 5(b) respectively. As
seen in the figures, the frequency-dependent conductiv-
ity plots show two distinct regions. The first region ob-
served at low frequencies corresponds to the frequency-
-117-
Fig. 5. (Color online) Conductance spectra of (a) PEG:
Mg(CH3 COO)2 with different salt concentrations at 303 K
and (b) 85PEG: 15Mg(CH3 COO)2 polymer electrolyte at dif-
ferent temperatures.
independent conductivity. This conductivity value has
been assigned to the bulk conductivity of the sample
(σdc ). In the high-frequency region, the conductivity
increases with increasing frequency. The σdc value has
been calculated from the extrapolation of the plateau
region to the Y-axis, and the values are listed in Ta-
ble 1. The maximum conductivity was found to be 1.06
× 10−6 S/cm at 303 K for the 85PEG:15Mg(CH3 COO)2
polymer electrolyte. The dc conductivity values ob-
tained from conductance spectra have been found to co-
incide with the bulk conductivity values obtained from
the impedance plot. Figure 5(b) shows that the ionic
conductivity of the polymer electrolyte increases as the
temperature increases due to the dissociation of ion ag-
gregations at higher temperatures.
Figure 6 shows the temperature-dependent conduc-
tivity of the polymer electrolytes with the best ionic
conductivity in each system studied through impedance
measurements for temperatures ranging from 303 K to
333 K. From Fig. 6, the polymer electrolytes can be seen
to show an Arrhenius behavior as the ionic conductivity
is enhanced almost linearly with increasing temperature.
Miyamoto and Shibayama [13] explained that the ionic
conductivity increased with increasing temperature as a
result of the free volume model where, as the tempera-
-118-
Fig. 6. (Color online) Temperature dependence of the ionic
conductivity of PEG: Mg(CH3 COO)2 : (a) 100:0, (b) 95:05,
(c) 90:10, (d) 85:15, and (e) 75:25.
ture increases, the polymer electrolyte can expand eas-
ily and produce free volume. Therefore, ions, solvated
molecules, or polymer segments can move into the free
volume, causing it to increase [14]. This enhances the
ion and the polymer segmental mobility, which will, in
turn, enhance the ionic conductivity.
IV. CONCLUSION
A polymer electrolyte of pure PEG and PEG com-
plexed with Mg(CH3 COO)2 has been prepared by using
the solution-casting technique. XRD and FTIR spec-
troscopy confirm the formation of the polymer-salt com-
plex. The system of poly (ethylene glycol) doped with
15-wt-% magnesium acetate had the highest conductiv-
ity, 1.07 × 10−6 S/cm, at room temperature (303 K).
The temperature dependence of the ionic conductivity
revealed an Arrhenius-type thermally activated process.
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Journal of the Korean Physical Society, Vol. 59, No. 1, July 2011
ACKNOWLEDGMENTS
One of the authors Mr. Anji Reddy Polu gratefully
acknowledges the financial support of University grant
commission (UGC) for a meritorious research fellowship.
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