Ionics (2012) 18:65–73
DOI 10.1007/s11581-011-0588-5
ORIGINAL PAPER
Electrical conductivity, electrical modulus, and scaling
studies of Li2O–Ga2O3–P2O5 glass electrolyte doped
with selenium ions
Ch. V. Koti Reddy & R. Balaji Rao & K. Chandra Mouli &
D. V. Rama Koti Reddy & K. Veera Bhadra Rao
Received: 7 December 2010 / Revised: 21 March 2011 / Accepted: 31 March 2011 / Published online: 14 June 2011
# Springer-Verlag 2011
Abstract A serious of glass samples according to the
formula (100−x) (0.5 Li2O−0.2Ga2O3 −0.3P2O5)+x SeO2
(x=0, 2, 4, 6, 8, 10 and 12 mol%), labeled as LGPSx (x is
the mole percent of SeO2) were synthesized through melt
quenching technique. Glass transition temperature Tg and
Hurby’s parameter for the prepared LGPS samples were
characterized by DSC Traces. FTIR and Raman spectra
indicated that SeO2 acts as either glass modifier (SeO32−) or
glass former (SeO42−) as the composition of SeO2 changes.
The best bulk conductivity, the highest conductivity is
achieved by the LGPS10 sample (σ=1.605×10−6 S/cm, at
303 K). The variation of conductivity with frequency of
glass samples was explained in the light of different
oxidation states of selenium ions. The super curve in the
scaling analysis suggesting the temperature independent
relaxation phenomenon.
Keywords AC conductivities . FTIR . XRD . Ionic
conductivities . Glasses
C. V. K. Reddy : K. C. Mouli : D. V. R. K. Reddy
Department of Engineering Physics,
A. U. College of Engineering,
Visakhapatnam, Andhra Pradesh, India
R. B. Rao (*)
Department of Physics, GITAM University Hyderabad Campus,
Hyderabad, India
e-mail: rbr_309@gitam.edu
K. V. B. Rao
Pujya Shri Madhavanji Institute of Science and Technology,
Hyderabad 501 359, India
Introduction
Interest on highly ionic conducting lithium phosphate glass
electrolytes has been increased in recent years owing to
their technological significance in solid-state batteries,
electrochromic devices, microelectronics, solid electrolytes,
reference electrodes, and also in optical devices [1–3].
Among these applications, performance and characteristics
of glasses are strongly dependent on composition, impuri-
ties, thermal stability, and electrochemical stability. The
addition of Li2O into phosphate glass system, which acts as
network modifier and breaks P–O–P linkages, introduces
coordinated defects along with non-bridging oxygen sites.
Generally, Li+ ions sit in the vicinity of these non-bridging
oxygen sites, and ionic conductivity is believed to arise
from non-random hopping of Li+ ion between these sites
under the influence of an external field. Among the oxides
of IIIA group elements, gallium oxide is found to be a good
stabilizer of phosphate glasses. Gallium oxide was reported
to occupy in network modifying sites or network forming
sites of lithium phosphate glass network leading to
variation in the structural changes and alter the electrical
properties such as electrical conductivity, electrical modu-
lus, activation energy and relaxation, etc., of the glass
network significantly [4]. In view of the technological
importance, we have selected the gallium oxide as
intermediate compound to stabilize in the lithium phosphate
glass network. On the other hand, we have selected SeO2 as
a dopant to extend the applicability of this glass electrolyte
for the technological applications. SeO2 is one of the most
important semiconductors which possess attractive features
desired for various applications in photonics and electron-
66
ics, too [5, 6]. It is reported that selenium oxide possesses
two kinds of structures as selenite and selenate around Se
atom. Selenite (SeO32−) acts as a modifier in the glass
network with three coordinated oxygen and one lone pair of
electron, whereas the selenate (SeO42−) with four coordi-
nated oxygen occupies tetrahedral sites in the glass network
and acts as a network former [5, 6]. However, the main
difficulty in the synthesis of glasses mixed with higher
SeO2 content is the rapid volatilization from selenite liquids
and the sublimation of SeO2 at atmospheric pressure and
glass transition temperature around 318 °C. Besides the
volatility, the other main obstacle for practical applications
is their hygroscopy; to overcome this problem, the research
has focused on smaller concentrations of SeO2 in Li2O–
Ga2O3–P2O5 glass network so that physical characteristics
like chemical resistance, electrochemical stability, thermal
stability, refractive index, thermal expansion coefficient,
glass transition temperature, and infrared transmittance
are improved and are further expected to increase the
range of practical utility of these glasses. The desired
properties of LGPS glasses can be achieved by choosing
the suitable concentration of SeO2 to make them suitable
for advanced technology applications. Reports on the role
of SeO2 in various glass matrices are available in the
literature [5–9]. Based on FTIR and Raman spectra, it was
concluded that selenium ions due to SeO32– and SeO42–
groups act either as glass modifier or former with the SeO2
content in the LGPS glass network. Among all the glass
samples synthesized with different compositions in our
laboratory, the present compositions showed the superior
electrical properties with a very low degree of hygroscopic
nature.
The objective of the present investigation is to explore
the influence of SeO2 on Li2O–Ga2O3–P2O5 glasses using
DSC, FTIR, Raman spectra, and electrical properties as a
function of frequency and temperature. They were also
studied through impedance spectroscopy in view of the fact
that this technique is a powerful tool to probe in the glass
materials [10–12].
Experimental description
Analytical reagent-grade chemicals of Li2CO3, P2O5,
Ga2O3, and SeO2 were thoroughly mixed in an agate
mortar and melted in a platinum crucible at 600±10 °C for
about 2 h until a bubble-free liquid was formed. The
resultant melt was then quenched in a stainless steel mould
and subsequently annealed at 300 °C. The amorphous state
of the glasses was checked by X-ray diffraction spectra
recorded on PANanalytical diffractometer B.V fitted with
copper target and nickel filter operated at 40 kV, 30 mA.
Differential scanning calorimetric studies (for determining
Ionics (2012) 18:65–73
glass transition temperature Tg) on these samples were
carried out by using TA instruments DSC 2010 differential
scanning calorimeter with a programmed heating rate of
20 °C min−1 in the temperature range of 30–600 °C to an
accuracy of ∼0.1 °C. The experimental error on the glass
transition temperature determination for these glasses was
found to be ±3 °C. The FTIR transmission spectra of these
glasses in KBr matrices were recorded by using Perkin–
Elmer 283B spectrophotometer in the wave number range
of 1,400 to 200 cm−1, with an ordinate accuracy: ±1.0%.
Raman spectra were obtained by using a Raman spectro-
photometer with the pumping beam of He–Ne laser (λ=
632.8 nm) with a resolution fixed at 1.5 cm−1 for the whole
set of measurements. The spectra were measured between
200 and 1,400 cm−1. A thin coating of silver paint was
applied (to the larger area faces) on either side of the
glasses to serve as electrodes for electrical measurements.
Real (Z′) and imaginary (Z″) parts of the impedance of
present glasses were obtained by using a Solartron 1260
Impedance/Gain-Phase analyzer controlled by personal
computer in the frequency range of 10–106 Hz at room
temperature and as well as temperatures from 303–423 K
with a 10-K temperature step.
Results and discussion
DSC studies
Figure 1 shows the DSC thermograms for all the samples of
LGPS glass system. The homogeneity of those glasses is
indicated by the single peak due to the glass transition
temperature (Tg) in DSC pattern of all the glass samples
prepared. It can be seen that the glass transition temperature
Tg is decreased from 0 to 10 mol% of SeO2 content (from
LGPS0 to LGPS10). However, beyond this concentration,
the value of Tg is increasing rapidly. This observation
indicates that the highest de-polymerization occurred for
the glass network labeled LGPS10. The parameter Kgl =(Tc −
Tg)/(Tm −Tc) introduced by Hurby’s, is not an absolute
indicator of the glass forming ability; being scan-rate
dependent, it is only a measure of the ease of vitrification
[13]. According to Thomburg, the variation of Kgl with the
scanning rate result is the strong dependence of onset
temperature, while glass transition temperature and melting
temperature remains nearly constant, and it was proved that
for good glass-forming systems, the value of Kgl ≥0.1.
Hurby’s parameter (Kgl) is a good estimate of the glass-
forming tendency; the higher this value, the more stable the
glass is and less critical is the quenching rate [13]. The
lowest value of Kgl (inset of Fig. 1) for LGPS10 indicates
the highest degree of disorder of the glass network as the
selenium ions may prefer to occupy network modifying
Ionics (2012) 18:65–73 67

∼1,042, ∼711, ∼605, and ∼545 cm−1 for LGPS0 glass

Fig. 1 DSC traces for all the samples of LGPS glass system
positions within the favored concentrations. The variation
of parameters Tg, Tm, Tc, Tg/Tm, (Tc –Tg)/Tg and (Tc –Tg)/Tm
for all those glass compositions are listed in Table 1.
FTIR spectra
Infrared and Raman spectra are both related to changes in
vibrational and rotational energy levels, being complement
to each other because the intensity of the spectral band
depends on the efficiency of the photon energy transferred
to the molecule through different mechanisms. Moreover,
these techniques are non-destructive, requiring only small
amount. Most of the research on vibrational spectroscopy
of phosphate glasses gives information on their structure
obtained in terms of oxygen bridges and terminal groups
rather than in terms of polyhedra. Notably, it is the (PO2)−,
(PO3)−2, and (PO4)3− groups, rather than the separate
groups P=O and P–O groups, that manifest themselves in
the vibrational spectra of meta- pyro- and ortho-phosphate
and also of phosphate glasses related to the corresponding
composition changes. The FTIR spectra of LGPS glass
samples are shown in Fig. 2. The bands cited at ∼1,234,
sample are shown in Fig. 2, and their modification of
intensity with the shift of all the band positions from the
glass sample LGPS0 to LGPS10 are as follows (Fig. 2): (1)
band cited at ∼1,234 cm−1 is identified due to asymmetric
stretching vibration of P=O bond and a remarkable shift of
this band is from lower to higher wavenumber (1,234–
1,267 cm−1); (2) significant change in the band cited at
∼1,042 cm−1 from lower to higher wavenumber (1,042–
1,074 cm−1) is assigned to stretching vibration of PO43−
tetrahedra; (3) weak absorption band cited in between
(∼711–720 cm−1) is attributed to the bending vibration of
P–O–P/Se linkage [7]. Intensity of these bands (P=O, PO43−,
P–O–P/Se) are observed to decrease with increasing SeO2
content from 0 mol% (LGPS0) to 10 mol% (LGPS10);
beyond this concentration, the trend is reversed. Neverthe-
less, a band cited at ∼545 cm−1 observed in all the glass
samples is ascribed to O=P–O vibrations [14], and network
forming GaO4 groups [14] have also exhibited a vibrational
band at ∼605 cm−1. The band positions and their intensity of
O=P–O vibrations and GaO4 groups remain unaltered [14].
In addition to these bands, a band observed at (∼916–
881 cm−1) from LGPS2 to LGPS10 glass samples is ascribed
due to symmetric stretching vibration of isolated pyramidal
SeO32− groups, leading to the formation of Se–O–Se bridges.
Intensity of this band is observed to increase with a shift
toward lower wavenumber (916–881 cm−1) from the glass
sample LGPS0 to LGPS10. The increasing trend in the
intensity of this band obviously indicates the increasing
modifying action of the selenite groups (SeO32−) in the glass
network with increasing SeO2 content from 0 mol% (LGPS0)
to 10 mol% (LGPS10); beyond this concentration the trend is
reversed (Fig. 2) [7]. The bands corresponding to the
network forming selenate groups (SeO42−) were not identi-
fied properly in all the LGPS glass samples from FTIR
spectra (Fig. 2); hence, Raman spectra for all the samples has
been recorded and analyzed, which will be described in the
next section.
Therefore, the information obtained from FTIR spectra
gives the interactions between the Li+ ions, phosphate glass
network, and the network modifying selenium ions and it is
helpful in order to understand the formation of non-

Table 1 Summary of DSC

data for all the samples of LPG Glass Tg (K) Tc (K) Tm (K) Tg/Tm (Tc-Tg)/Tm (Tc-Tg)/Tg Kgl=(Tc-Tg)/(Tm-Tc)
glass system
LGPS0 742 829 980 0.757 0.117 0.089 0.576
LGPS2 731 825 991 0.738 0.129 0.095 0.566
LGPS4 725 818 1,000 0.725 0.128 0.093 0.511
LGPS6 720 820 1,018 0.707 0.139 0.098 0.505
LGPS8 715 809 1,010 0.708 0.131 0.093 0.468
LGPS10 690 789 1,038 0.665 0.143 0.095 0.398
LGPS12 705 800 1,021 0.690 0.135 0.093 0.430
68 Ionics (2012) 18:65–73

[14–16]. The bands cited at lower frequencies, which are in

Fig. 2 FTIR spectra for all the samples of LGPS glass system
bridging oxygen sites and the ionic transport phenomena in
these glasses. Details of band positions of FTIR spectra of
all the LGPS glass samples are listed in Table 2.
RAMAN spectra
Raman spectra of the glass samples in the frequency range of
200–1,400 cm−1 was shown in Fig. 3. Raman analysis of
LGPS glasses shows the main features with the most
prominent bands. The strongest band in the region
(∼1,053–1,077 cm−1) in all the LGPS samples is due to
symmetric stretching modes of non-bridging (PO2)sym−
oxygen atoms, whereas the bands cited in between (∼724–
753 cm−1) due to bridging (P–O–P/Se)sym oxygen atoms
betweeen (∼395–418 cm−1), assigned to the PO4 bending
vibrations [14]. The intensity of abovementioned bands due
to symmetric vibrations of the (PO2)sym− and (P–O–P/Se) sym
is found to decrease from the glass sample LGPS0 to
LGPS10. However, the band due to bending vibrations of
PO4 units is observed to increase; this trend is reversed from
LGPS10 to LGPS12. The band attributed to rocking modes of
networking-forming GaO4 tetrahedra occurring in the wave-
number ranges from 618 cm−1. The intensity and position of
band due to GaO4 structural groups at ∼618 cm−1 remains
unaltered for all the LGPS glass samples [14]. The spectra of
these glasses have also exhibited an additional bands
ascribed to Se–O vibrations due to selenite groups (SeO32−)
and selenate groups (SeO42−) cited at ∼895 and 930 cm−1 for
the glass sample LGPS2. Intensity of a band cited at
∼895 cm−1 due to selenite groups (SeO32−) from lower to
higher wavenumber ∼(895–870 cm−1) obviously suggests
the increasing network modifying action of selenite groups
(SeO32−) in the glass network from sample LGPS0 (0 mol%
of SeO2) to LGPS10 (10 mol% of SeO2); beyond this
concentration, the trend is reversed. The decreasing trend in
the intensity of the band due to selenate groups (SeO42−)
cited at 930 cm−1 from lower to higher wavenumber ∼(930–
944 cm−1) obviously indicates the increasing network
forming action from the glass sample with 0 mol% of
SeO2 (LGPS0) to 10 mol% of SeO2 (LGPS10); beyond this
concentration the trend is reversed. Hence, the Raman
spectral studies indicate that as the SeO2 content increases
from 0 to 10 mol%, the difference in coordination between
Se cation and P cation leads to an increase in the
concentration of non-bridging sites of the lithium phosphate
glass network. This statement clearly suggests that at lower
concentrations of SeO2 (up to 10 mol%), the selenium ions
are due to SeO3 groups prefer to occupy the network

Table 2 Assignments of the FTIR and Raman bands in the spectra of all the LGPS glass samples

Band positions IR assignments Raman assignments

Wavenumber (cm−1)

IR Raman

(∼395–418) Bending vibrations of PO4 units

∼545 O=P–O vibrations
∼605 ∼618 GaO4 tetrahedral groups Rocking modes of GaO4 tetrahedral groups
∼(711–720) ∼(753–724) Bending vibrations of P–O–P/Se linkages Bridging (P–O–P/Se)sym oxygen atoms
∼(881–916) ∼(870–895) Symmetric stretching vibration of isolated Se–O vibrations due to (SeO32−) groups
pyramidal (SeO32−) groups
∼(930–944) Tetrahedral (SeO42−) groups
∼(1,074–1042) ∼(1,053–1077) Stretching vibrations of PO43− tetrahedral groups Symmetric stretching modes of non-bridging (PO2−)
sym oxygen atoms
∼(1,234–1,267) Asymmetric stretching vibrations of P=O bonds
Ionics (2012) 18:65–73 69

Fig. 3 Raman spectra for all the samples of LGPS glass system

modifying positions and create more non-bridging sites in

the glass network leads to increase in the de-polymerization
of glass network. The creation of non-bridging sites in the
PO4 units reveals the shifting of the Raman band positions
and change in its intensity of the present glass samples. The
detailed information in Raman spectra is supportive in order
to understand the electrical conductivity and relaxation
response of these glasses. Increase in the network modifying
isolated selenium groups observed from the sample LGPS0
to LGPS10 via FTIR and Raman spectra will lead to the
structural modification of glass network, which will be
discussed in the next section. Details of band positions of
Raman spectra of all the LGPS glass samples are listed in
Table 2.
Electrical conductivity and relaxation behavior
Fig. 4 Impedance spectra Z″ versus Z′ for all the samples of LGPS
system measured at 303 K
obtained from the analyzed impedance data and pellet
dimensions were used to calculate the bulk conductivity of
all the glass samples at 303 K and for the highest
conducting glass sample LGPS10 at different temperatures.
The bulk conductivity can be calculated by taking
sample geometry into account as follows:
s ¼ ð1=RÞ  ðt=AÞ ð1Þ
where t/A is the sample geometric ratio, t is the sample
thickness, and A is the electrode area used to measure the
properties of the sample. Using the above equation, one can

The electrical properties for all the LGPS glass samples

were monitored by using impedance spectroscopy. This
technique operates an alternating current with variable
frequency and when measurements are carried out as a
function of frequency and temperature, it is possible to
determine the activation energies of the conduction and
dielectric relaxation processes. The complex impedance
plots (Z″ vs. Z′) of all the glass samples measured at 303 K
and for the highest conducting sample LGPS10 at different
temperatures (303–423 K) were found to exhibit complete
semicircles, as depicted in Figs. 4 and 5. The bulk
resistance (R) for all the samples relative to each experi-
mental temperature is deduced from the intercept of
imaginary Z″ impedance with real Z′ impedance axes. The
impedance data obtained in this analysis was fitted to
nonlinear least square method. Hence, the electrical
Fig. 5 Impedance spectra Z″ versus Z′ for all the samples of LGPS
properties can be associated to a parallel resistance–
system measured at 303 K. Inset shows compositional dependence of
capacitance (RC), equivalent circuit, and therefore, bulk conductivity log (σ) and activation energy (Eaσ) for all samples of
response of the glass is detected. The resistance (R) LGPS system measured at 303 K
70 Ionics (2012) 18:65–73

deduce that the highest conductivity is achieved by the

LGPS10 sample (σ=1.605×10−6 S/cm at 303 K).
In Fig. 5, we show the characteristic complex impedance
plots at different temperatures for the highest conducting
sample LGPS10, where it can be seen that the increase in
temperature caused the impedance semicircles to be shifted
to lower and lower Z′ values. Once again, one can use the
intersection points of the imaginary impedance onto the real
axis of semicircles to use Eq. 1 to calculate the bulk
conductivity of all the glass samples as a function of
temperature. The bulk conductivities calculated from the
analyzed impedance data obtained at different temperatures
for all the glass samples are plotted in Fig. 6 (shown as log
σT versus 1,000/T). Fig. 7 log (σ) vs. log (f) plots for all the samples of LGPS system
measured at 303 K. Inset shows the variation of characteristic
The conductivity data is fitted to the Arrhenius equation
parameter (s) with the conc. of SeO2 at 303 K
s dc ¼ s 0 expðEas =kTÞ ð2Þ
conductivity; the nonlinearity between the conductivity
σ0 is the pre-exponential factor and Eaσ, k, and T are the and the activation energy suggests that the conductivity
activation energy for the conduction, Boltzman’s constant enhancement is directly related to the activation energy
and absolute temperature, respectively. The activation barrier [17]. Selenium ions can be considered as immobile
energy for conduction (Eaσ) was calculated from the slope within the time window of hopping processes of the alkali
of the straight lines, and it was obtained when the data was (Li+) ions; the contribution to the conduction for the
plotted against 1,000/T of all the glass samples with various glasses investigated in this paper can be attributed mainly
compositions (Fig. 6). The composition dependence of due to motion of Li+ ions [18]. This is further affected by
conductivity (log σ) and the activation energy (Eaσ) at the presence of the network modifying isolated selenium
303 K is shown in the inset of Fig. 5. It is observed that the groups (SeO32−) which will be described next. It was
activation energy is found to be the minimum and reported that our glass samples revealed the presence of
conductivity is highest for glass sample LGPS10 (10 mol% Li2O in the glass network. The results in the formation of
of SeO2). Since the inset of Fig. 5 (activation energy (Eaσ), large number of non-bridging sites, where the Li+ ions are
vs. SeO2 content) does not show the nonlinear behavior of weakly bonded to non-bridging sites. On the other hand,
lone pair structure of network modifying selenium ions
due to isolated SeO32− groups also enhances the de-
polymerization of glass network. As it appears, due to the

Fig. 8 log (σ) vs. log (f) plots for highest conducting sample LGPS10
sample measured at different temperatures (303–423 K). Inset shows
Fig. 6 log(σT) vs. 1,000/T for all the samples of LGPS system the normalized spectra of conductivity for highest conducting sample
measured at 303 K (LGPS10) sample measured at different temperatures (303–423 K)
Ionics (2012) 18:65–73 71

Table 3 Summary of conduc-

tivity, activation energy, charac- Glass σ (403 K)S/cm Eaσ (eV) s (403 K) Eaτ (eV) β (403 Κ) τ (10−4 s) 403 K
teristic parameter, and critical
frequency, relaxation time for all LGPS0 2.83E−08 0.598 0.644 0.698 0.543 0.489
the compositions of LGPS glass LGPS2 4.50E−08 0.565 0.618 0.682 0.538 0.766
system LGPS4 8.26E−08 0.548 0.587 0.605 0.522 1.352
LGPS6 1.45E−07 0.531 0.565 0.598 0.519 1.892
LGPS8 1.60E−07 0.521 0.542 0.581 0.509 2.123
LGPS10 1.60E−06 0.513 0.531 0.549 0.501 2.515
LGPS12 6.83E−08 0.555 0.611 0.591 0.528 1.112

highest modifying action of selenium ions for composi-
tions up to 10 mol% of SeO2, easy paths for the movement
of the charge carriers are created, and hence, increase in
the conductivity is observed. However, from LGPS10 to
LGPS12, the conductivity is observed to decrease gradu-
ally with corresponding increase in activation energy as a
result of large repulsion between the same Li+ ions and
may be due to blocking of network forming SeO42− groups
by rigidly bound Li+ ions. Hence, the variation of
conductivity with concentration of lithium and co-
valence of selenium ions depends heavily on the structural
modifications of the glass system [5].
In order to evaluate conductivity non-linearities, it is
useful to present the ac conductivity for all the composi-
tions of LGPS glass system. The dependence of the
electrical conductivity with the frequency can be analyzed
by the power law equation:
s ac ¼ s 0 þ A w s
ð3Þ
where σ0 is the conductivity at zero frequency, which is
normally termed the dc conductivity, A is a constant and s is
a characteristic parameter (0<s<1). The low frequency part
of the conductivity is normally frequency-independent, and
the frequency-independent conductivity σ0 is obtained by
extrapolation of the conductivity to ω= 0. The high-
frequency part of the conductivity exhibits the dispersion
and increases in a power-law fashion [19]. Typical plots of
Fig. 9 Variation of log τ with 1,000/T for all the samples of LGPS
glass system
ac conductivity as a function of frequency at 303 K for all
LGPS glass samples are presented in Fig. 7. Similarly, the
ac conductivities for the highest conducting glass sample
LGPS10 at different temperatures are shown in Fig. 8. The
values of σ0 or σdc obtained for all the samples at 303 K
(from Fig. 7) are listed in Table 3. From Fig. 7, it can be
seen that the critical frequency (ωp =fo), at which the
conductivity deviates from the frequency-independent part
change with the SeO2 content. The change in the critical
frequency is more obvious for the ac conductivity of
LGPS10 at different temperatures presented in Fig. 8.
Nevertheless, the relation between frequency-independent
conductivity σ0 and the critical frequency (fo) can be
represented by the following equation:
s0 ¼ K f o; ð4Þ

where K=(Ne2a2/kT)νc(1-c) is the empirical constant, ν is
the geometrical factor which include correlated factor, c is the
concentration of mobile ions on N equivalent lattices per unit
volume, a is the hopping distance, e is the electronic charge,
T is absolute temperature, and k is Boltzman’s constant,
which depends on the concentration of mobile ions,
temperature, and the conduction mechanism [20, 21].
It has been observed that the relaxation effects begin to
appear at the critical frequency (fo) and move towards the
higher frequency within the wider experimental frequency
range. Furthermore, it is observed that the critical frequency
(fo) is thermally activated with same activation energy as σ0
T [22]. The characteristic parameter(s) has been observed to
be material-dependent and calculated from the Eq. 3. The
composition dependence of characteristic parameter(s) is
shown in the inset of Fig. 7, and it is observed that the “s”
is found to be lowest for the highest conducting LGPS10
glass sample. The minimum value of “s” is found to be
related to the high degree of modification and is found to be
dependent on the concentrations of network modifying ions
in the glass network [23]. However, the increasing value of
“s” from LGPS10 to LGPS12 is due to the presence of the
ions that are present predominantly in network forming
sites at higher concentrations. The frequency-independent
part of the conductivity may be attributed due to the long-
range transport of Li+ ions, and the frequency-dependent
72
part of the conductivity could be explained through
diffusion-controlled relaxation model [24]. The summary
of electrical conductivity, activation energy, and character-
istic parameter is listed in Table 3.
Another approach to probe the electrical response of
materials containing some degree of ionic conductivity, which
is to use the complex electric modulus Μ*(ω)=Μ′+j Μ″,
where Μ′ is the real part of the electric modulus and Μ″ is the
imaginary part of electric modulus. This formulation is
predominantly appropriate to identify phenomena as electrode
polarization and bulk phenomenon such as average conduc-
tivity relaxation times τσ [25, 26]. Εlectrical modulus data,
(M″ vs. log (f) plot) of all the LGPS glass samples measured
at different temperatures 303–423 K, suggested that the Μ″
value is observed to be constant (Μ″max) at a relaxation
frequency (fmax) and the peak Μ″max symmetrically shifts
towards higher frequencies with increasing temperatures.
The relaxation frequency (fmax) corresponding to maximum
in M″ curves and the relaxation time τ was calculated using
the relation τ=1/2π fmax at different temperatures can be
obtained.
The experimental data are well-described by the Arrhe-
nius expression, given as below:
t ¼ t 0 expðEat =T kÞ ð5Þ
where τ0 is the pre-exponential factor and Εaτ is the
activation energy for conductivity relaxation.
The variation of log τ with 1,000/T for all the LGPS
glass samples at different temperatures is shown in Fig. 9. It
can be observed that the relaxation time (τ) symmetrically
shifts to lower values with an increase in temperature. The
activation energy for the conductivity relaxation Eaτ of all
the glass samples was calculated from the relaxation time
plots. It was observed that activation energies for relaxation
(Εaτ) were slightly higher than thermal activation energies
(Εaσ). This statement obviously suggests the presence of
possibly small degree of contribution of electronic conduc-
tion mechanism; however, this contribution does not
influence the overall conductivity response that much in
the LGPS glass samples.
Scaling analysis
Scaling analysis is a characteristic element for any data
evolution program. Inset of Fig. 8 is presented to
demonstrate that the mechanism of ion transport in the
glass system is unaffected by composition and tempera-
ture. In this figure, the ac conductivity data obtained at
various temperatures for LGPS10 is scaled with character-
istic frequency (f0) and the frequency-independent con-
ductivity σ 0 of the frequency axis (x-axis) and ac
conductivity axis (y-axis) [27–29]. From inset of Fig. 8,
it is observed that all the curves observed at different
Ionics (2012) 18:65–73
temperatures fit in to a single super curve; this super curve
suggests that the present glass samples show confirmation
of the temperature-independent conduction transport
mechanism.
Conclusions
The lowest values of glass forming ability parameter (Kgl),
and the glass transition temperature (Tg) for the highest
conducting sample LGPS10 in the DSC studies indicate the
highest de-polymerizability. FTIR and Raman spectral
studies revealed the presence of network modifying
selenium ions in the LGPS glass network due to isolated
selenite (SeO32−) groups up to 10 mol% of SeO2; beyond
this concentration, selenium ions seems to occupy the
network forming sites due to selenate (SeO42−) groups with
four coordinated oxygen occupy tetrahedral sites in the
LGPS glass network. The bulk conductivity of highest
conducting sample LGPS10 was determined as 1.605×
10−06 S/cm at 303 K. The activation energy (Eaσ) and
power-law exponent (s) were calculated to be 0.513 eV,
0.533 for the highly conducting glass sample LGPS10. The
single super curve in normalized plots of ac conductivity in
the scaling analysis suggests that the present glass samples
follow temperature-independent conductivity distribution
relaxation mechanism. In addition, the glass electrolyte
with highest conductivity (LGPS10) would be a better
candidate for solid-state device applications
References
1. Martin SW, Angell CA (1986) J Non Cryst Solids 83:185–207
2. Muralidharan P, Nallamuthu N, Prakash I, Satyanarayana N (2007)
J Am Ceram Soc 90(1):125
3. Isaac A, Hadzifejzovic E (2000) Solid State Ionics 134:249
4. Fu J (1998) J Mater Sci 33:1549
5. Lee CH, Sohn HJ, Min Gyu Kim T (2005) Solid State Ionics
176:1237
6. Lee CH, Joo KH, Kim JH, Woo SG, Kang T, Park Y, Oh JY (2002)
Solid State Ionics 149:59
7. Yanko B, Dimitriev S, Yordanov I, Luben I (1995) J Non Cryst
Solids 192–193:179
8. Dimitriev Y, St Y, Lakov L (2001) J Non Cryst Solids 293:410
9. Venkateswarlu M, Satyanarayana N, Rambabu B (2000) J Power
Sourc 85:224
10. Kluvanek P, Klement R, Karacon M (2007) J Non Cryst Solids
353–356:2004
11. Mogus-Milankovic A, Santic A, Karabulut M, Day DE (2003) J
Non Cryst Solids 330–334:128
12. Grac MPF, da Silva MG Ferreira, Sombra ASB, Valente MA
(2007) Physica B 62–69:396
13. Hruby A, Czechoslovak (1972) J Phys 22:1187
14. Little Flower G, Srinivasa Reddy M, S. Baskaran G, Veeraiah N
(2007) Optical Materials 30:357
15. Le Saou G, Simon P, Fayon F, Vaills Y (2002) J Raman Spectros
33:740
Ionics (2012) 18:65–73
16. Fang X, Ray CS, Mogus A, Day DE (2001) J Non Cryst Solids
283:162
17. Muthupari S, Raghavan SL, Rao KJ (1996) J Phys Chem
100:4243
18. Rolling B, Ingram MD (2002) J Non Cryst Solids 265:113
19. Nobre MAL, Lafendri S (2001) J Phys Chem Solids 62:1999
20. H. Jain, O. Kanert, (1993) In; J. M. Spaeth (Eds.). Proceedings of the
XII, International Conference on Defects in insulting materials, vol.1,
World Scientific Co.: 274
21. Jain H, Hsieh CH (1994) J Non Cryst Solids 172:1408
73
22. Verhoef AH, Denhartog HW (1994) Solid State Ionics 68:305
23. Veeranna Gowda VC, Anavekar RV (2005) Solid State Ionics
176:1393
24. Elliot SR, Owens AP (1994) Solid State Ionics 70:27
25. Almond DP, West AR (1983) Solid State Ionics 11:57
26. Gerhardt RA (1994) J Phys Chem Solids 55:1491
27. Moynihan CT, Boesch LP, Laberge NL (1973) Phys Chem Glasses
14:122
28. Ghosh A, Pan A (2000) Phys Rev Lett 84:2188
29. Schroder TB, Dyre JC (2000) Phys Rev Lett 84:310