Solid State Ionics 147 (2002) 249 – 257

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Polymer electrolytes and polyelectrolytes:

Monte Carlo simulations of thermal effects on conduction
J.F. Snyder *, M.A. Ratner , D.F. Shriver
Department of Chemistry and Materials Research Center, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113, USA

Abstract

Monte Carlo calculations were carried out to simulate ion diffusion through polymer matrices. A dynamic bond percolation
(DBP) model was employed that includes local harmonic motion of covalently bound anions in polyelectrolyte systems. The
temperature dependence of cation diffusion was investigated in polyelectrolytes and polymer – salt complexes for 0 – 100
C.
Systems in which the rate of polymer reorganization is independent of temperature display Arrhenius behavior both above and
below the Tg of 35
C. Systems in which the temperature is coupled to the rate of polymer reorganization display VTF behavior
above the Tg and near Arrhenius behavior below the Tg. In all cases, the temperature is coupled to the rate of successful ion
jumps. Temperature and Tg seem to have no effect on the ion density at which the cation conductivity reaches a maximum.
D 2002 Elsevier Science B.V. All rights reserved.

Keywords: Polymer electrolyte; Polyelectrolyte; Ion conductivity; Temperature dependence; Monte Carlo simulations; Dynamic bond
percolation model

1. Introduction complexes and polyelectrolytes. In polymer – salt

There has been considerable interest in polymer
electrolytes since Armand et al. [1] recognized their
potential application in solid state batteries [2,3].
These systems are not limited by the volatility of
liquid electrolytes or the brittleness of traditional solid
electrolytes. In addition, they can function as the
electronic separator between the electrodes [4]. Sol-
vent-free single-phase polymer electrolytes may be
classified into two major categories, polymer – salt
*
Corresponding authors. J.F. Snyder is to be contacted at
Tel.: +1-847-491-3461; fax: +1-847-491-7713. M.A. Ratner. Tel.:
+1-847-491-5652; fax: +1-847-491-7713.
E-mail addresses: snyderj@chem.nwu.edu (J.F. Snyder),
ratner@chem.northwestern.edu (M.A. Ratner).
complexes, both ion species are free to diffuse
through the system. In polyelectrolytes, one ion is
covalently bound to the polymer. For systems in
which the anion is bound, there is an inherent cation
transference number of one. This property deters salt
buildup in lithium ion batteries. For polyelectrolytes
in the present study, the anions are restricted and the
lithium cation is the only independently mobile spe-
cies. It has been established that solvent-free poly-
electrolyte systems can produce reasonable ambient
temperature conductivities (10
5 S/cm) [5]. The
target conductivity for commercially viable lithium
batteries ( > 10
3 S/cm) has not yet been attained with
these types of materials when they are free of small
molecule solvents. It has been demonstrated that ion
diffusion occurs principally in the amorphous phase
of polymer electrolytes [6], but the details of ion

0167-2738/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 7 - 2 7 3 8 ( 0 2 ) 0 0 0 2 5 - 5
250 J.F. Snyder et al. / Solid State Ionics 147 (2002) 249–257
transport are not well understood. We have modeled
transport phenomena to understand the mechanistic
differences between polymer – salt complexes and
polyelectrolytes, and to explore the dependence of
conductivity on temperature and anion motion.
Considerable effort is being devoted to the theo-
retical study of polymer electrolytes through the use
of molecular dynamics [7– 11]. The studies of ion
dynamics presented here have been performed using
Monte Carlo calculations, which do not have the
advantages (full dynamics) or the computational lim-
itations (short times) of molecular dynamics. Many
previous attempts to describe ion motion have used
free volume type ideas [12 – 14]. Our model is based
on the dynamic bond percolation (DBP) model [15 –
17], which instead presents a largely microscopic
description of motion in polymer electrolytes. The
DBP model incorporates the theory of static percola-
tion [18,19], which depicts particle motion as hopping
between neighboring sites on a lattice. Particle diffu-
sion relies on a randomly chosen set of available
pathways, labeled ‘bonds’. Through these pathways,
each particle has on average, access to a predeter-
mined number of adjacent sites. In the DBP model,
the lattice sites represent ion coordinating sites on a
polymer, and the bonds represent the possibility of
hopping to adjacent sites. Elastomeric motion is
simulated by periodically redistributing or ‘repercolat-
ing’ the bonds at a time sR. The rate of redistribution
is proportional to the rate of segmental rearrangement
and accordingly models the dependence of ion trans-
port on polymer motion. First-order chemical kinetics
can describe the rate of hopping using the master
equation:
dPi X
¼ ðPj Wji
Pi Wij Þ
dt j
where Pi is the probability of an ion being found at
site i and Wij is the rate of ion motion from site i to site
j. Lonergan [20] extended the DBP theory to include
charged particles.
Ion correlation can have a detrimental effect on
cation diffusion. When both species are freely mobile,
the cations and anions can move in pairs or small
clusters resulting in reduced conductivity and devia-
tion from Nernst – Einstein behavior [21,22]. Addi-
tionally, since the anions are often more freely dif-
fusive, the cation transference number is frequently
observed to be less than 0.5. Polyelectrolytes prevent
these problems by prohibiting counterion diffusion.
However, clusters may still form around the immobile
anions. Cations can be trapped in local potential wells
[20], reducing the overall conductivity. We have pre-
viously shown, through an improvement to the DBP
model [23,24], that local anion motion in polyelec-
trolytes can significantly diminish the negative effects
of ion correlation and improve cation conductivity,
while retaining unit cation transference number. By
means of this improvement, a broad range of polymer
electrolytes has been simulated and cation conductiv-
ity was shown to be optimized as a function of anion
local motion and total ion density. In this current
work, we further investigate ion correlation through
the use of this extended DBP model. In particular, the
effects on cation conductivity are examined as a
function of temperature, in the range of 0 – 100
C.
The effects on cation conductivity for both polyelec-
trolytes and polymer – salt complexes are examined in
cases when the temperature is either coupled or not
coupled to the rate of polymer rearrangement. Cation
conductivity is also studied at a variety of ion/site
densities at several temperatures.
2. Simulations
Our model was recently described [23,24] and it is
very similar to the one used by Lonergan [20 – 22,25].
The sites of a rigid lattice gas model represent sites on
the polymer that coordinate ions, such as etheric oxy-
gens. Ions occupy the sites and diffuse through the
matrix by hopping. The lattice currently employed is
square planar (two-dimensional) with periodic boun-
ð1Þ
daries. The size of the lattice was varied in conjunc-
tion with the number of ions to determine the ion
density. The smallest lattice used contains 2025 sites
(density = 0.5 – 0.9 ions/site) and the largest lattice
contains >105 sites (density = 0.01 ions/site). The lat-
tice length is given as a multiple of the intersite spa-
cing. Results from the smallest lattices were verified
through simulations using larger lattices. No finite
size effects were observed. The configurations of the
system can be expressed by
n ¼ fn1 ,n2 , . . . nN g ð2Þ
 J.F. Snyder et al. / Solid State Ionics 147 (2002) 249–257 251

Using this notation, the potential energy for the

system is given by:
XN X N
ni nj q2
Esys ðnÞ ¼ : ð4Þ
i¼1 j>i
4pe0 erij

In Eq. (4), N is the total number of sites, q is the

ion charge, e is the selected dielectric constant, and rij
is the distance between sites i and j. Charge neutrality
is maintained by fixing qcation =
qanion. Experiments
are averaged over at least five independent simula-
tions to improve statistical accuracy. Except where
noted, the standard deviation of the data points is
within the symbol size. During each simulation, the

Fig. 1. These are two representations of the same data set. Cation
diffusion increases rapidly from the backbone polyelectrolyte value
to the polymer – salt complex value with only a minimal range of
anion motion. (a) Investigates this increase as a function of the
range of anion motion. (b) Explores it as a function of the force
constant H on a logarithmic scale. The data points are fit to a B
spline function. The simulations in this data set were run for 104
Monte Carlo Steps at T * = 0.25 with an ion density of 0.20 ions per
lattice site. The error bars on (a) are shown for both the cation tracer
diffusion coefficient (labeled as Dt) and the anion mean squared
displacement. The error was derived from statistical deviation of the
five simulations over which each data point was averaged.

where
8
>
>
1 anion occupation
>
>
<
ni ¼ 0 vacant : ð3Þ Fig. 2. T * = 0.25, ion density = 0.20. (a) Relates the rate of attemp-
>
> ted jumps that are successful, or blocked by other ions, with the
>
>
: force constant H. Error is within symbol size. (b) Examines the
1 cation occupation relative coulomb energy per particle for these same simulations.
252 J.F. Snyder et al. / Solid State Ionics 147 (2002) 249–257

Fig. 3. T * = 0.25. Cation/anion distribution functions for several ion densities. The solid line represents the polyelectrolyte limit and the dotted
line represents the polymer – salt complex limit. The data points are fit to spline functions.

system was evolved through randomly selected single where DEsys(n) follows from Eq. (4), ri is the position
particle hops from site i to nearest neighbor site j with of site i, and H is an effective harmonic force constant
probability per unit time Probij. Following the general that binds each moving anion to its initial position r0
scheme of percolation theory, Wij is set to 1 if the bond [24]. For freely mobile anions, H is 0, while for rigidly
is available and 0 if it is not. Since coulomb inter- bound anions, H is infinity. In all systems studied here,
actions were included, the Metropolis transition prob- the cations are freely mobile (Hcations = 0).
ability [26,27] was used for unblocked jumps to insure Each system was equilibrated over three consec-
the proper equilibrium distribution. Thus Probij is: utive steps: (1) high temperature annealing with
8 Wij = 1 for all i and j; (2) equilibration under exper-
>
> exp½
DEij =kB T  for DEij > 0 imental temperature, but retention of Wij = 1 for all i
>
> and j; (3) equilibration with experimental temperature
<
Probij ¼ 1 for DEij V0 and bond allowances. Equilibration is indicated by
>
> fluctuation of the lattice energy around a mean value.
>
>
:
0 for nj a0,Wij ¼ 0 The appropriate values of H were applied during all
ð5Þ stages of equilibration. Once equilibrium was reached,
the systems were allowed to evolve for 104 Monte
where DEij refers to the overall change in energy in Carlo time steps (MCS), for each of which there was
the move, expressed by: Nm jump attempts. Bonds were periodically redistrib-
uted to simulate polymer segmental motion. The time
Ej
Ei ¼ DEij ¼ DEsys ðnÞ þ 2H ½ðrj
r0 Þ2 lengths of experiments allowed convergence of the
properties of the system. Coulomb interactions were

ðri
r0 Þ2  ð6Þ calculated by Ewald summations [28,29]. Reduced
 J.F. Snyder et al. / Solid State Ionics 147 (2002) 249–257 253

Fig. 4. Temperature dependence of cation conductivity at ion density = 0.30 ions/site. (a) Includes systems in which the polymer segmental
motion is not coupled to temperature. The time between bond renewals is 10 MCS in all cases. The behavior is Arrhenius. (b) Studies the effect
of coupling temperature to polymer motion. The time between bond renewals was calculated for each temperature by means of Eq. (8). The
parameters are otherwise identical to those in the simulations in (a). There is VTF-like behavior at temperatures above the Tg and Arrhenius
behavior (within the error of the simulations) at temperatures below the Tg.
254 J.F. Snyder et al. / Solid State Ionics 147 (2002) 249–257
units were used throughout so distances are given in
terms of the intersite lattice spacing, a; and thermal
energy in terms of reduced temperature T * = kbT/e(a),
where e(a) = q2/(4pe0ea).
3. Results
Several experimentally realizable parameters were
varied to explore cation diffusion as a function of
temperature for different anion mobilities. Simulations
were run at eight different total (anion plus cation)
particle densities ranging from 0.01 to 0.9 for temper-
atures ranging from T* = 0.183 to T * = 0.25. These
temperatures correlate to a range of 0 –100
C for
e(a) = 2.060
10
20 J. In a system with screened
charges, this could correspond to a = 5 Angstroms and
e = 5.6. In comparison to real polymers, ePEO  5 [30]
and ePPO = 5.78 [31]. The bond density was set to 0.35
on a square planar lattice, which is well below the
static percolation limit of 0.50 for square planar
lattices [32]. This guarantees that significant long-
range ion diffusion depends on periodic redistribution
of the bonds, as is the case in real polymer electrolytes
[6]. The time between bond repercolations, s, was set
to be 10 MCS for one set of data, and adjusted
according to temperature for others. A repercolation
time that is independent of temperature would be
expected to result in conductivity that exhibits Arrhe-
nius behavior, whereas a temperature-dependent
repercolation time should result in conductivity that
displays VTF type behavior. s is represented by [33]:
A
s ¼ ce T
T0
where c is a constant, kBA is an activation energy and
T0 is the temperature at which free volume goes to
zero. A was set to 878 K. T0  Tg
50 K. T0 was set
to
15
C in all simulations here. This corresponds
to the T0 elucidated from the (PEO)5LiSCN system
[1]. s was set to be 10 MCS for T * = 0.25 (T = 100

C). In simulations in which renewal was coupled to
temperature, s can be calculated for other temper-
Fig. 5. Dependence of cation conductivity on ion concentration at three temperatures. The minima at the endpoints arise respectively from a very
low concentration of charge carriers and from severely reduced diffusion at high concentrations owing to blockage. The maxima occur at
different ion concentrations for the polyelectrolyte and polymer – salt complex limits. The simulations in (a) were run at T * = 0.25 (T = 100
C).
The temperature is reduced in (b) to T * = 0.2232 (T = 60
C), and in (c) to T * = 0.1964 (T = 20
C). Tg = f 35
C.
atures by using s1 = s(T1 = 100
C) = 10 MCS in the
equation:
A A

T
s2 ¼ s1 e T2
T0 1
T0 : ð8Þ
For each set of parameters, the relative changes in
conductivity were compared for Hanion in both the
backbone polyelectrolyte limit (H ! infinity) and the
polymer – salt complex limit (H ! 0). At the comple-
tion of each simulation, the time-dependent mean
squared displacement (MSD), h (Dx(t))2i, was calcu-
lated for each ion species from the migration of the
particles over the simulation time. The MSD can be
directly related to the tracer diffusion coefficient:
hðDxðtÞÞ2 i
Dt ¼ ð9Þ
2dt
where d represents the dimensionality. d = 2 in all
cases here. Dt can be used to find the conductivity, r,
through the corrected Nernst –Einstein equation:
1 nq2 Dt
r¼ ð10Þ
HR kB T
where HR = Dt/Dr is the Haven ratio [20], a factor that
compensates for ion correlations. Dr is the actual
conductivity diffusion coefficient. HR was set to 1
for all calculations.
Fig. 1 shows a significant dependence of ion motion
on the force constant, H. Fig. 1a suggests that for a
density of 0.2 ions/site, the most significant growth in
cation Dt occurs when the anion motion initially
changes from frozen to local motion—a range of three
lattice sites, roughly 1.5 nm. This compares favorably
ð7Þ
with previous results calculated using s = 100 MCS
[24], which have additionally indicated that the cation
conductivity will increase faster with increasing anion
motion as the system becomes more dense. Very li-
mited anionic motion can still generate a substantial
increase in cation conductivity. Fig. 1b reveals a near
logarithmic increase in ion mobility as the restrictions
defined by H on the anions are relaxed. The slopes for
the two ion species are very similar, but they do not
J.F. Snyder et al. / Solid State Ionics 147 (2002) 249–257 255
256 J.F. Snyder et al. / Solid State Ionics 147 (2002) 249–257
overlap one another. Furthermore, cation diffusion in-
creases over a range of H in which there is no long-
range anion motion—that is, while the anions are still
‘‘tied down’’ to their sites of origin. This shows that the
increase in cation diffusion is due to something other
than increased mobility of ionic pairs and clusters.
Fig. 2 explores this phenomenon further. The solid
line in Fig. 2a plots the variation in the rate of success
for attempted jumps for each species. The dotted line
traces the rate of unsuccessful jumps that resulted
from physical blockage by another ion. The error is
within symbol size. Although Fig. 1b indicates that
there is no long-range anion movement at high values
of H, Fig. 2a shows that local motion does occur. In
fact, the cation diffusion curve in Fig. 1b appears to
correlate well with this rate increase in anion success-
ful jumps. There also appears to be an inverse
correlation between the rates of successful jumps
and blocked jumps for cations. That is, the fluctuation
in successful jumps is caused both by energetic effects
and by physical blocking. This suggests a strong
initial increase in clustering, which is supported by
the energy/particle minimum at H = 100 in Fig. 2b.
Fig. 3 compares the degree of clustering at either
limit of H over the range of simulated particle
densities by means of the cation –anion radial distri-
bution function g(r). At low and moderate densities,
including d = 0.2 ions/site, there is significant cluster-
ing. As the concentration of ions is raised, the large
first peak in g(r) is reduced and the systems begin to
resemble one large cluster with distributions that are
characteristic of glassy substances. In the case of
polymer –salt complexes, the system equilibrates into
a highly ordered ion – counterion –ion network. In the
polyelectrolyte limit, this network is hindered by the
initial, random placement of static anions so a highly
ordered system is precluded.
To understand better the role of temperature
dependence in polymer electrolyte systems, two types
of systems were simulated. In one, temperature is
coupled only to ion jumps. That is, only the temper-
ature and force constant H were varied. The time of
bond repercolation was set to be independent of
temperature (10 MCS in all simulations). In the
second type of system, temperature is coupled to
polymer segmental motion as well as anion mobility
[34 – 36]. That is, the time of bond repercolation was
recalculated for each temperature by means of Eq. (8).
As the temperature decreases, polymer motion slows
down and the rate of bond repercolation decreases.
Below a certain temperature (Tg), the lattice is essen-
tially static. Polymer electrolytes are most effectively
modeled by means of this coupled expression.
Fig. 4 explores the behavior of these two types of
systems studied. In Fig. 4a, the temperature is coupled
to ion jumps alone. Arrhenius behavior for the cation
conductivity is evident in both the polymer – salt com-
plex and polyelectrolyte limits. The slopes of the
conductivity curves appear to be independent of anion
mobility. In Fig. 4b, the temperature is also coupled to
temperature by means of polymer renewal. Above the
Tg (chosen to be 35
C) there is clear VTF behavior.
Below the Tg, the lattice is essentially static and the
conductivity curve displays Arrhenius behavior (with-
in the error of the simulations). This is reasonable since
long-range cation diffusion is coupled to polymer seg-
mental motion.
Fig. 5 investigates the dependence of cation con-
ductivity on ion density for three temperatures. All of
these simulations were of the second type; that is, the
rate of bond renewal was coupled to the temperature.
All of the curves are effectively zero at the endpoints
and show a maximum in between. At very low ion
densities, there are very few charge carriers so the con-
ductivity is effectively zero. At very high densities, the
systems become so crowded the ions have nowhere to
move. In our previous studies [24], we have noticed
that the maximum conductivity in polymer – salt elec-
trolytes is at a higher density than that for polyelec-
trolytes. This shift is apparent here as well. Inter-
estingly, temperature and the Tg do not seem to affect
this shift. Fig. 5a and b are above the Tg and Fig. 5c is
below the Tg. Temperature does affect the relative
increase in conductivity between the two curves. At
lower temperatures, anion mobility seems to make a
more significant difference in cation conductivity. This
can be attributed to a greater influence of anion trap-
ping on cation diffusion as the temperature is lowered.
4. Conclusions
We have found that the nature of cation conduc-
tivity is highly dependent on effective temperature,
the rate of bond repercolation, particle density, and
local anion mobility. A substantial fraction of the
 J.F. Snyder et al. / Solid State Ionics 147 (2002) 249–257
conductivity difference between polyelectrolytes and
polymer – salt complexes can be regained by allowing
for local anion motion in polyelectrolytes. The minor
range of anion motion required to promote significant
changes in cation conductivity suggests this would
still retain a unit cation transference number. Poly-
electrolytes in which the anion is on the terminal end
of a flexible side chain [37] may undergo local motion
as described in this model. The flexibility and length
of the side chain shape the degree of anionic ‘‘bind-
ing’’ described by the force constant H in these
studies, i.e. the boundaries of the local motion. The
ratio of anionic side chains to etheric oxygen side
chains determines the ion density of the system.
Arrhenius behavior is evident in the systems for
which temperature is not coupled to polymer rear-
rangement. In the systems for which the rate of poly-
mer rearrangement is dependent on temperature, VTF
behavior is apparent for temperatures above the Tg,
and Arrhenius behavior is noticeable below the Tg. The
nature of anion mobility does not seem to affect the
nature or slope of these curves. Anion mobility affects
the ion density dependence of conductivity though, in
that the conductivity maximizes at a higher density for
polymer – salt complexes than for polyelectrolytes.
These maxima are unaffected by temperature or
whether the system is above or below the Tg. Com-
parable simulations on cubic lattices are underway.
Acknowledgements
This work was supported by the U.S. Department
of Energy, LBL, the ARO, and the Northwestern
Materials Research Center. We would also like to
thank Dr. Abraham Nitzan for his help and insight in
this work.
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