Polymer International Polym Int 50:89±94 (2001)

Study of a new polymer electrolyte

poly(ethylene oxide): NaClO3 with several
plasticizers for battery application
R Chandrasekaran and S Selladurai*
Solid State Ionics Laboratory, Department of Physics, MIT campus, Anna University, Chromepet, Chennai-600 044, Tamil Nadu State,
India

Abstract: Sodium ion conducting thin ®lm polymer electrolytes based on poly(ethylene oxide) (PEO)
complexed with NaClO3 were prepared by a solution-casting method. Characterization by XRD, IR
spectroscopy and AC conductivity has been carried out on these thin ®lm electrolytes to analyse their
properties. The conductivity studies show that the conductivity value of PEO:NaClO3 complex
increases with the increase in salt concentrations. Increase in conductivity was found in the electrolyte
system by the addition of low molecular weight polymer poly(ethylene glycol) (PEG) and the organic
solvents dimethylformamide (DMF) and propylene carbonate (PC). Using these electrolyte systems,
cell parameters were measured from the discharge study with the application of load 100 kV at room
temperature with common cell con®guration NajelectrolytejC:I2:electrolyte. The open circuit voltage
(OCV) ranges from 2.81 to 3.23 V and the short circuit current (SCC) ranges from 340 to 1180 mA.
# 2001 Society of Chemical Industry

Keywords: polymer electrolyte; PEO; PEG; conductivity

INTRODUCTION (eg propylene carbonate (PC), diethyl carbonate

Interest in solid polymeric electrolytes has increased (DEC), ethylene carbonate (EC) and dimethyl carbo-
the number of ion-conducting materials because of nate (DMC)), studies on which have been reported
their possible applications (such as thin-®lm forma- earlier.16±21 Enhanced conductivity was also obtained
tion, interfacial contacts and desirable sizes) as solid by using low molecular weight poly(ethylene glycol)
electrolytes in advanced high-energy electrochemical (PEG).22 Keeping this in view, the authors report here
devices, eg batteries, fuel cells, electrochemical devices the effect of plasticizers on polymer conductivity and
and photo-electrochemical solar cells poly(ethylene on cell performance by using polymer electrolytes
oxide) (PEO) in particular is an exceptional polymer based on PEO and NaClO3 salt with the addition of
which dissolves a wide variety of salts to form the plasticizers PEG, PC and DMF. XRD and IR
polymeric electrolytes; the chemical stability of the spectral analysis were used to characterize the resulting
ether functional group strengthens the superiority of polymer electrolytes.
PEO as a host for a solid polymer electrolyte.1±7
Temperature-dependent conductivity studies, surface
analysis, glass transition temperature, structural EXPERIMENTAL
changes, and cell studies of many sodium-ion-con- The starting materials PEO (Aldrich, Mw = 5 
ducting polymer electrolytes based on PEO poly(pro- 106 g molÿ1), PEG (Aldrich, Mw = 4000 g molÿ1) and
pylene oxide) (PPO) and poly(bis-methoxyethoxy- NaClO3 were dried well. Polymer thin ®lms of
ethoxy phosphazene) (MEEP) complexed with, approximate thickness (100±140 mm) have been pre-
NaClO4, NaSCN, NaCF3SO3, NaPF6, NaI, NaYF4 pared by a solution-cast technique.23 Thin PEO:Na-
and NaNO3 have been reported earlier.8±15 To obtain ClO3 ®lms were prepared in the following molar ratios
moderate properties of polymer electrolytes (such as 90:10, 80:20 and 70:30 by a solution-cast technique
increase in conductivity, a wide redox stability, low using water-free methanol as solvent. To improve the
melting point, change in amorphous phases, increase conductivity of polymer electrolytes, PEG was intro-
in ionic mobility, decrease in viscosity, high ability to duced into the PEO:NaClO3 matrix. Thin ®lms of
dissolve salts), a new trend is the addition of PEG:PEO:NaClO3 30:60:10, 45:45:10 and 60:30:10
plasticizers to the corresponding host polymers. Most were prepared using the solution-cast technique.24
plasticizers are low molecular weight organic solvents The prepared plasticized polymer electrolyte reduced

* Correspondence to: S Selladurai, Solid State Ionics Laboratory, Department of Physics, MIT Campus, Anna University, Chrompet, Chennai-
600 044, Tamil Nadu State, India
E-mail: [email protected]; [email protected]
(Received 1 February 2000; revised version received 7 June 2000; accepted 30 June 2000)

# 2001 Society of Chemical Industry. Polym Int 0959±8103/2001/$30.00 89

R Chandrasekaran, S Selladurai

the crystallinity of the host polymer by a particular with that of the pure PEO system shows that the
amount. Adding the solvent PC±DMF to the plasti- intensity of diffraction peaks between 18.5 ° and 19 °
cized polymer electrolyte made the electrolyte more (2y) decreases with an increase of salt concentration. A
amorphous. The ®lms were similarly prepared using a sharp peak in the pure pattern at 2y = 23±25.7 °
solution-cast technique for PEG:PEO:NaClO3 ‡ PC decreases and broadens with increasing salt concen-
(10 w%) PEG:PEO:NaClO3 ‡ DMF (10 w%), but tration, and it was also found that the original peak of
only PEO:NaClO3 (90:10) was used for PEG, PC pure PEO is shifted in the complexed PEO pattern.
and DMF studies. This shows a decrease in the degree of crystallinity of
Polymer±salt complexation was con®rmed by using the polymer with the addition of salt. The sharp peak
both X-ray diffraction and IR techniques for PEO- in the complexed PEO spectrum shows that the
based electrolytes. The XRD investigations were per- complexed PEO is not fully amorphous, especially in
formed using a Seifert diffractometer (2y up to 60 °). the case of PEO:NaClO3 (70:30) which has additional
The result is given in chart form showing a record of peaks at around 2y = 29 ° and 9 ° resulting from
counts per second, ie proportional to diffracted beam increased levels of NaClO3 salts. The XRD observa-
intensity, versus diffraction angle 2y. The IR spectra of tions show that the crystalline nature of the PEO is
the ®lms were recorded by using a Hitachi 270-50 reduced by the addition of salt. Generally, the X-ray
FTIR spectrophotometer over the range 450± diffraction studies show that the amorphous character
4000 cmÿ1. A Chen-Hwa model 1061 LCZ bridge of the polymer increases as addition of salt increases,
was used for measuring conductivity values in AC up to a certain limit.3
methods by applying a frequency range 0.04±200 kHz
at various temperatures in the range 303 to 378 K. IR studies
Here, impedance and phase angle were measured as a The IR spectra of pure PEO, and different ratios of
function of frequency and temperature for each PEO complexed with NaClO3 were recorded. The
composition. The data was analysed in two standard following changes were observed: (i) in pure PEO, the
ways, ie Arrhenius plots (log s) versus 1000/T where intense peak around 2950 cmÿ1 due to aliphatic CÐH
linear regions are identi®ed, and complex impedance stretching decreases with the addition of salt; (ii)
plots (Zcosy versus Zsiny) where arcs of circles are changes in the 1100 cmÿ1 region of PEO due to
®tted, to give the bulk resistance (Rdc) of the corre- stretching and bending vibrations of CÐC bonds and
sponding electrolyte. The electrical conductivity is CÐOÐC stretching vibrations in the complexed
subsequently obtained from the relation PEO; (iii) changes in pure PEO peaks at around
1200±1300 cmÿ1 due to CÐO stretching vibrations in
 ˆ …t=Rdc A†
the presence of salts; and (iv) peak changes in PEO on
where t is the thickness of the pellet, and A is the area either side of 1400 cmÿ1 due to CH2 bending in the
of the cross-section of the cylindrical pellet. complexed electrolyte. There is much broadening of
Finally, using these polymer electrolytes, the elec- the polymer composite peaks, illustrating the weak
trochemical cells were fabricated in the con®guration interactions of the polymer with NaClO3. In addition,
NajElectrolytejC ‡ I2 ‡ electrolyte for all electrolytes at the same interaction between NaClO3 and PEO is
room temperature. Under vacuum conditions, the revealed in the XRD patterns; decrease of peak
anode material (negative electrode), sodium metal, intensity is noted with increasing salt concentration.
was taken in the form of a thin (around 1 mm) slice. From this observation, it is con®rmed that the changes
This sodium metal slice was placed on a copper plate, found in the XRD and IR spectra are due to the
the electrolyte was placed on the sodium metal and the addition of NaClO3 to PEO.
cathode material was placed on the electrolyte.
Another copper plate was placed on the top of the AC conductivity studies
cathode. Those copper plates were used as current From the AC conductivity measurements, the con-
collectors. Finally, the cell was sealed under vacuum. ductivity values were calculated for all samples at
Composite cathode material (C (50 %) ‡ I2 (50 %) ‡ different temperatures. The conductivity curves are
electrolyte (10 %)) was used in the form of pellets of shown in Figs 1±3. The conductivity values of pure
thickness around 1.2 mm. This composite cathode has PEO, PEG, PEG:PEO (1:1) and NaClO3 are 0.98 
been used to modify the open circuit voltage, gives 10ÿ9, 7.26  10ÿ7, 5.12  10ÿ7 and 1.8  10ÿ4 S cmÿ1,
stable current drain and increases the SCC value.14,15 respectively, at 35 °C. The conductivity value slowly
Under load, the cells were discharged at room tem- increases with an increase of temperature for all four
perature. systems. Usually for PEO:salt complexes, the con-
ductivity values are in the range of 10ÿ3±10ÿ4 S cmÿ1
at 80±100 °C, falling in the range 10ÿ6±10ÿ8 S cmÿ1 at
RESULTS AND DISCUSSION room temperature. The ionic transport in the PEO±
XRD studies MX complexes may be interpreted on the basis of a
The complexation of NaClO3 salt with pure PEO was hopping mechanism between polymer chains.3,5 From
con®rmed by XRD and IR spectral studies. The XRD the conductivity measurements the following results
pattern of the PEO:NaClO3 system when compared were obtained. At room temperature, the conductivity

90 Polym Int 50:89±94 (2001)

 PEO: NaClO3 polymer electrolytes

Figure 1. Conductivity versus inverse

temperature plot for PEO:NaClO3
(90:10) (&), PEG:PEO:NaClO3
(30:60:10) (~), PEG:PEO:NaClO3
(30:60:10) ‡ 10 % PC (*), and
PEG:PEO:NaClO3 (30:60:10) ‡ 10%
DMF (!).

Figure 2. Conductivity versus inverse

temperature plot for PEO:NaClO3
(90:10) (&), PEG:PEO:NaClO3
(45:45:10) (~), PEG:PEO:NaClO3
(45:45:10) ‡ 10 % PC (*), and
PEG:PEO:NaClO3 (45:45:10) ‡ 10%
DMF (!).

of PEO increases sharply in the PEO:NaClO3, of the PEG:PEO:NaClO3 system but lower than that
PEG:PEO:NaClO3 and PEG:PEO:NaClO3 ‡ PC/ of the PEG:PEO:NaClO3 ‡ DMF system. Of the four
DMF (10 w%) systems. The magnitude of change is systems of electrolytes, PEG:PEO:NaClO3 ‡ DMF
of the order of 104±102 times when compared with systems have higher conductivity values. This may be
pure PEO. The conductivity of the PEO:NaClO3 because the dimethyl amide group aids association
system increases 100-fold upon addition of PEG, with the parent polymer. The increase in conductivity
possibly because of the reduction in the viscosity of the values for electrolytes containing PC and DMF are
PEO±salt complexes. The conductivity of the small because their percentage in PEG:PEO:NaClO3
PEG:PEO:NaClO3 ‡ PC system is higher than that is small.21 The linear variation seen before and after

Figure 3. Conductivity versus inverse

temperature plot for PEO:NaClO3
(90:10) (&), PEG:PEO:NaClO3
(60:30:10) (&), PEG:PEO:NaClO3
(60:30:10) ‡ 10 % PC (*), and
PEG:PEO:NaClO3 (60:30:10) ‡ 10%
DMF (!).

Polym Int 50:89±94 (2001) 91

R Chandrasekaran, S Selladurai

Table 1. Activation energies (eV) for poly(ethylene oxide) based systems for cells based on PEO:NaClO3 (Fig 4a) and
Electrolyte system Region I Region II PEG:PEO:NaClO3 (Fig 4b) at room temperature
with the application of 100 kO. Half cell reactions are
PEO:NaClO3 (90:10) 0.539 0.260
as follows: at the anode Na→ Na‡ ‡ eÿ; at the cathode
PEO:NaClO3 (80:20) 0.527 0.444
I2 ‡ 2eÿ→2Iÿ and Na‡ ‡ Iÿ→NaI.
PEO:NaClO3 (70:30) 0.383 0.438
PEG:PEO:NaClO3 (30:60:10) 0.391 0.287
From the cell studies, the following results are
PEG:PEO:NaClO3 (45:45:10) 0.361 0.215 obtained. In the case of higher salt content polymer
PEG:PEO:NaClO3 (60:30:10) 0.417 0.215 electrolyte, ie (70:30) ratio, the cell discharge time
PEG:PEO:NaClO3 (30:60:10) ‡ PC 0.432 0.340 decreases because of the rapid formation of a layer at
PEG:PEO:NaClO3 (45:45:10) ‡ PC 0.300 0.274 the site of the electrode, chain mobility is restricted by
PEG:PEO:NaClO3 (60:30:10) ‡ PC 0.360 0.250 higher salt concentration, and ion-pairing effect also
PEG:PEO:NaClO3 (30:60:10) ‡ DMF 0.403 0.257 takes place.5 The maximum open-circuit voltage
PEG:PEO:NaClO3 (45:45:10) ‡ DMF 0.339 0.197 (OCV) was found in the PEO:NaClO3 (90:10)-based
PEG:PEO:NaClO3 (60:30:10) ‡ DMF 0.428 0.187 cell. The maximum short-circuit current (SCC) value
was observed for the added electrolyte DMF. The
addition of PEG gave better cell performance than
the melting region shows an Arrhenius type of PEO-based electrolytes, but higher concentrations of
thermally activated process. The measured Ea values PEG lead to very small changes of the cell parameters.
are given in Table 1. Decreasing Ea values show that The energy density values of (PEG ‡ PC ‡ DMF)-
plasticizers reduce the crystalline nature of the poly- based electrolytes have 2±3 times higher energy
mer±salt complexes, and this is also re¯ected in density than pure PEO-based electrolytes. In contrast
increasing ionic conductivity values. In general, at to the OCV value, the discharge time, energy density
higher temperature the conductivity value increases and SCC values were higher in (PEG:PEO)-based
because the internal modes are activated, ie semicrys- electrolytes than in PEO-based electrolyte. A small
talline electrolytes change into amorphous ones. This percentage of the electrolytes PC or DMF added to the
is particularly evident at polymer melting. polymer do not change the cell parameters, which
closely resemble those of PEO:PEG electrolytes. From
Cell studies the cell discharge hours it is clear that cyclic carbonates
Discharge curves from the electrochemical cells were have a great plasticizing effect in polymer electrolytes.
observed at 35 °C. Typical curves are shown in Fig 4 The various parameters evaluated are summarized in

Figure 4. Cell discharge characteristic

curves for (a) PEO:NaClO3 (90:10)
(&), PEO:NaClO3 (80:20) (*) and
PEO:NaClO3 (70:30) (~), (b)
PEG:PEO:NaClO3 (30:60:10) (&),
PEG:PEO:NaClO3 (45:45:10) (*) and
PEG:PEO:NaClO3 (60:30:10) (~).

92 Polym Int 50:89±94 (2001)

 PEO: NaClO3 polymer electrolytes

Electrolytes
PEO:NaClO3 PEO:NaClO3 PEO:NaClO3
Cell parameter at 35 °C (90:10) (80:20) (70:30)
Area of cell (cm2) 0.95 0.95 0.95
Wt of cell (g) 0.81 0.94 0.92
OCV (V) 3.23 3.05 2.96
SCC (mA) 340 586 810
Current density (mA cmÿ2) 358 617 853
Discharge time (h)b 92 85 68
Discharge capacity (mA hÿ1) 3.7 6.89 11.9
Power density (W kgÿ1) 1.356 1.901 2.606
Energy density (W h kgÿ1) 124.7 161.6 177.2
a
Table 2. Various cell parameters for PEO:NaClO3 Cell con®guration: NajelectrolytejC ‡ I2 ‡ electrolyte.
b
systemsa Cut-off voltage for all cells is around 1.50 V.

Electrolytes
PEG:PEO:NaClO3 PEG:PEO:NaClO3 PEG:PEO:NaClO3
Cell parameter at 35 °C (30:60:10) (45:45:10) (60:30:10)
Area of cell (cm2) 0.95 0.95 0.95
Wt of cell (g) 0.72 0.76 0.81
OCV (V) 3.12 3.08 3.0
SCC (mA) 460 590 680
Current density (mA cmÿ2) 484 621 716
Discharge time (h) 164 140 130
Discharge capacity (A hÿ1) 2.8 4.21 5.23
Power density (W kgÿ1) 1.82 2.39 2.53
Energy density (W h kgÿ1) 298 334.7 328.5
a
Table 3. Cell parameters for Cell con®guration: NajelectrolyteC:I2:electrolyte.
b
PEG:PEO:NaClO3 systemsa Cut-off voltage for all cells is around 1.5 V.

Tables 2±5. The contributions of plasticizers in these responsible for ion hopping in the polymer matrix.
electrolytes are mainly concern the SCC values, not (ii) Platicizers are mainly used to enhance the
the OCV values. conductivities of the corresponding electrolytes, but
make different contributions to their respective elec-
trolytes. (iii) The plasticizing effect of the low mol-
CONCLUSIONS ecular weight polymer with higher molecular weight
From the conductivity results, the following observa- polymer is limited. (iv) Addition of the solvents PC
tions are made. (i) Plasticizers (PEG, PC and DMF) and DMF to polymer electrolytes is used to increase
activate the polymer chain relaxation, which is their amorphous character and hence the conductivity

Electrolytes
PEG:PEO:NaClO3 PEG:PEO:NaClO3 PEG:PEO:NaClO3
Cell parameters at 30 °C (30:60:10) (45:45:10) (60:30:10)
Area of cell (cm2) 0.95 0.95 0.95
Wt. of cell (g) 0.79 0.84 0.82
OCV (V) 3.00 2.96 2.82
SCC (mA) 580 790 886
Current density (mA cmÿ2) 611 832 933
Discharge timeb (h) 176 159 143
Discharge capacity (mA hÿ1) 3.3 4.97 6.2
Power density (W kgÿ1) 2.2 2.78 3.05
Energy density (W h kgÿ1) 387 442 435
a
Table 4. Cell parameters for Cell con®guration: NajelectrolytejC:I2:electrolyte.
b
PEG:PEO:NaClO3 ‡ PC systemsa Cut-off voltage for all cells is around 1.5 V.

Polym Int 50:89±94 (2001) 93

R Chandrasekaran, S Selladurai

Electrolytes
Cell parameters at room PEG:PEO:NaClO3 PEG:PEO:NaClO3 PEG:PEO:NaClO3
temperature (30:60:10) (45:45:10) (60:30:10)
Area of cell (cm2) 0.95 0.95 0.95
Weight of cell (g) 0.73 0.76 0.78
OCV (V) 3.12 2.92 2.81
SCC (mA) 640 860 1180
Current density (A cmÿ2) 674 905 1240
Discharge timeb (h) 105 79 66
Discharge capacity (mA hÿ1) 6.1 10.9 17.8
Power density (W kgÿ1) 2.73 3.3 4.24
Energy density (W h kgÿ1) 287 261 280
a
Table 5. Cell parameters for Cell con®guration: NajelectrolytejC:I2:electrolyte.
b
PEG:PEO:NaClO3 ‡ DMF systemsa Cut-off voltage for all cells is around 1.5 V.

of the corresponding host polymer via chain relaxa- 7 Armand MB, In Polymer Electrolyte Reviews, Ed by MacCallum
tion. (v) From the discharge characteristic studies, it JR and Vincent CA Elsevier, London (1987).
8 Jaipal Reddy M, Sreekanth T, Ramalingaiah S and Subba Rao
was found that the electrolyte stability is higher for the
UV, J Power Sources 76:30±35 (1999).
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15 Sreekanth T, Jaipal Reddy M, Ramalingaiah S and Subba Rao
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94 Polym Int 50:89±94 (2001)