New all solid-state polymer electrolyte based on epoxy resin and

ionic liquid for high temperature applications

Luıs Carlos Oliveira da Silva , Bluma Guenther Soares
Federal University of Rio de Janeiro—UFRJ, PEMM-COPPE, Centro de Tecnologia, Rio de Janeiro, RJ 21941-972, Brazil
Correspondence to: L. C. O. da Silva (E - mail: lcos@metalmat.ufrj.br)

ABSTRACT: Flexible epoxy network loaded with high amount of ionic liquid (IL) 1-decyl-3-methylimidazolium bromide ([DMIM]Br)
has been reported by using a mixture of polyol amine as curing agent. The IL presents good electrochemical response even at 170 8C,
as no evidence of redox reactions was observed. The incorporation of as high as 50 wt % of this IL within the epoxy matrix resulted
in solid and flexible electrolyte with good thermal stability below 180 8C, as measured by thermogravimetric analysis and ionic con-
ductivity of around 1026 S cm21 at room temperature and higher than 1023 S cm21 at high temperature. This electrolyte presented
a prodigious potential for applications in electrochemical devices at high temperature like batteries and supercapacitors, and the flexi-
bility of this solid electrolyte persist at low temperature because of its low glass transition temperature. Furthermore, leakage prob-
lems were not observed. Thereby, impedance spectroscopy and cyclic voltammetry were performed to characterize the electrochemical
properties. VC 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 135, 45838.

KEYWORDS: batteries and fuel cells; electrochemistry; membranes; polyelectrolytes

Received 17 April 2017; accepted 25 September 2017

DOI: 10.1002/app.45838

INTRODUCTION organic or inorganic anions and present good chemical stability,

Polymeric materials have been used as an alternative for pro-
duction of electrolytes for several devices such as batteries,1 fuel
cells,2 and supercapacitors.3 Thermoplastic polymers, due to its
thermal and mechanical properties, were the first polymers to
be used for the production of polymeric electrolytes. However,
they present lower ionic conductivity, compared to conventional
liquid electrolyte, due to its complex structure and high viscosi-
ties.4 In spite of these drawbacks, their use is justified because
of the possibility of producing electrolytes with good mechani-
cal and thermal resistances and safer due to the lower risk of
leaks and the low flammability of polymers used for this pur-
pose compared to liquid electrolytes.
In electrochemical devices, the electrolyte has a very important
role, since its conductivity, potential window, and range of
working temperature determine the operating parameters of the
electrochemical devices.5 Thus, new polymeric electrolyte studies
looking for better performance and safety electrochemical devi-
ces have been more frequent in the literature.6
The use of ionic liquids (ILs) for the production of polymeric
electrolytes provided a great technological advance on the devel-
opment of electrochemical devices, because of their unique
properties. They are salts containing organic cations and
good thermal stability, low flammability, and low melting tem-
perature, usually less than 100 8C. In addition, the ILs present
good electrochemical stability and good conductivity values,
around 1023 S cm21 at room temperature.7,8 The conductivity
values of the ILs [EMIM]Cl, [EMIM]Br, [EMIM]BF4 and
[EMIM]PF4 at 25 8C were 0.24, 0.32, 15.71 and 4.91 (mS cm21)
respectively.9
Several studies have reported the efficiency of these polymeric
electrolytes based on thermoplastic polymers and ILs for use in
electrochemical devices.10–13 Peng et al.11 used thermoplastic
polyurethane and poly(vinylidene-co-hexafluoropropylene) with
a lithium salt for construction of an electrolyte for batteries,
obtaining an electrolyte with high conductivity, 6.62 3 1023
S cm21, and good mechanical stability at room temperature.
Thermoplastic polyurethanes were also used to produce super-
capacitors with high capacitance and high potential windows.12
A great drawback of using thermoplastic as polymer electrolytes
is their working temperature range, which is limited to the
melting point of the polymeric matrix. Therefore, the use of
thermosetting polymers to build electrolytes has been recently
increased. Some studies report the use of thermosetting gels as
electrolyte components.14–17 However, achieving good balance
of mechanical and electrical properties is not easy. Lower

Additional Supporting Information may be found in the online version of this article.
C 2017 Wiley Periodicals, Inc.
V

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crosslink density, which could improve the ionic mobility and
thus conductivity, also contributes for worse mechanical
strength and some problems like the leakage of the electrolyte at
higher temperatures. On the other hand, completely solid elec-
trolytes based on thermosetting polymer with high crosslink
density and high dimensional stability may present reduced
ionic mobility, resulting in a decrease in their conductivity.
Few papers have investigated the electrochemical and mechani-
cal behavior of epoxy-based electrolytes containing ILs. Shir-
shova et al. have used a series of IL–epoxy resin composites and
observed a conductivity as high as 1023 S cm21.18 However, the
electrolytes presented two phase separation at higher amount of
IL, which might be responsible for the leakage of ILs, mainly at
high temperature. Matsumoto and Endo have also combined
1-ethyl-3-methyl imidazolium bis(trifluoromethanesulfonyl)i-
mide as an IL in epoxy networked material constituted by a
mixture of bisphenol A diglycidyl ether and tetrafunctional
epoxy resins.19 They achieved good confinement of IL within
the epoxy network for systems with high crosslinking density
and an amount of IL up to 40%, with ionic conductivity corre-
sponding to around 1024 to 1025 S m21. To avoid or minimize
leakage problems, Matsumoto and Endo have developed flexible
epoxy network containing imidazolium-based IL covalently
attached to the polymer chain.20 The systems cured with poly(-
propyleneglycol) diamine or poly(ethyleneglycol) diamine exhib-
ited ionic conductivity from 1023 to 1025 S m21, depending on
the curing agent and the amount of IL. Also Nguyen et al.
developed an interesting system based on diepoxy-
functionalized 1,2,3-triazolium based IL cured with poly(propy-
leneglycol)diamine, obtaining ion conducting network with ion
conductivity in the range of 1027 S cm21.21
Considering the importance of this theme, we would like to
introduce in the present work another class of polymer electro-
lyte based on solid and flexible epoxy system with high crosslink
density, good thermal stability, and mechanical properties while
keeping good ionic mobility, thus guaranteeing high conductiv-
ity. For this purpose, imidazolium cation-based IL was used as
the ionic component in epoxy systems cured with a mixture of
polyetheramine with different molar mass (Jeffamine D-230 and
D-2000). The mixture of polyetheramine imparts flexibility to
the epoxy network, which is important for the conductivity.
Such epoxy-based polymer electrolytes have interesting and
potential application on the development of electrochemical
devices able to operate at high temperatures and could be used
as a sensor, as a battery, or as a capacitor in the oil and gas field
or other harsh environments application for example. The elec-
trochemical devices currently used do not work properly at
high temperatures, they usually work until 60 8C, the tempera-
ture where organic solvents could be used without significant
solvent lost. There are also some electrochemical devices, under
development, that use pure IL as electrolyte and could reach
high temperatures, however those devices present a liquid elec-
trolyte and consequently the risk of leakage. The electrochemical
device discussed in this work could work at high temperatures
(until 170 8C) as some IL devices and furthermore the electro-
lyte is in solid state increasing the safety of the device. Other
high temperature electrochemical devices were reported in the
45838 (2 of 8)
literature using different types of polymers and ILs to prepare a
solid electrolyte, however those devices do not reach a work
temperature as high as the temperature reported in this article.
With some adaptations, the electrolytes prepared in this work
can be used for supercapacitors, batteries, fuel cell membranes,
and hybrid energy sources. Hastak et al. (2012)22 produced
supercapacitors with different solid electrolyte concentrations
that have been fabricated and evaluated for their electrochemical
performance, their electrolytes have been based on phosphoric
acid-doped poly(2,5-benzimidazole). Solid polymer electrolytes,
corresponding to that used in the present work, have been used
as high temperature polymer electrolyte membrane for fuel
cell.23–27 Another system proposed was a polymer composite
electrolyte consisting of electrolyte using a three-dimensional
crosslinked polymer matrix, which is synthesized with poly(eth-
ylene glycol) and 3-glycidoxypropyl trimethoxysilane, and 1-
ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide as
a solid electrolyte for batteries.28 We can also use these high
temperature electrolytes for hybrid sources for an urban electric
vehicle for example.
The thermal stability and the degradation temperature of polymer
electrolytes were usually based on thermogravimetric analysis
(TGA) data.29 However, electrolytes made from thermoplastic pol-
ymers can be melted before their degradation temperature. Ther-
moset polymers cannot be melted because of their crosslinked
structures, then they can be used as electrolytes at higher tempera-
tures than the thermoplastic electrolytes since the degradation tem-
peratures of the thermoset polymer are higher than the
thermoplastic melting point.30 Other limitation of all IL-based
electrolytes is the thermal decomposition of IL. Thus, the electro-
lyte developed in this work presented a thermal degradation above
170 8C because all the components are stable until this tempera-
ture, and the limitans in that system it was the IL selected. More-
over, by changing the concentrations of jeffamines the properties
of the matrix can be modified and that will also effect the electro-
chemical properties. The same effect can be expected when the IL
is changed or combined with other ILs or inorganics salts. Conse-
quently, there is a composition that can help to develop a new
generation of energy storage devices, with higher temperature
range of use and more safety without leakage problems.
EXPERIMENTAL
Materials
Methylimidazole 99%, 1-bromodecane 98%, acetonitrile 99.8%,
and ethyl acetate 99.8% were purchased from Sigma Aldrich (S~ao
Paulo, Brazil). Diglycidyl ether of bisphenol A (DGEBA) based
epoxy prepolymer (EPON 828) (epoxy equivalent mass 5 188–
198 g mol21; viscosity 5 11–15 Pa s at 25 8C) was purchased
from Shell Chemicals do Brasil (S~ao Paulo, Brazil). Poly(propyl-
ene glycol) bis(2-aminopropyl ether) with molar mass of 230 and
2000 and amine equivalent mass of 60 and 514, respectively (D-
230 and D-2000) were purchased from Sigma-Aldrich. 1-Butyl-3-
methylimidazolium tetrafluoroborate 98% from Sigma-Aldrich
and trihexyl(tetradecyl)phosphonium bistriflamide (CYPHOS IL
109) from Cytec’s CYPHOS (S~ao Paulo, Brazil) IL were used as
commercial ILs.
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45838
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Synthesis of IL 1-Decyl-3-methylimidazolium bromide Table I. Formulations Used to Prepare the Electrolytes

The synthesis of the IL was carried out according to the meth-
odology adapted from the literature.7 In a typical procedure, Weight (g)
0.1 mol of methylimidazole and 0.15 mol of 1-bromodecane Electrolytes DGEBA JD230 JD2000 [DMIM]Br
were mixed in a three-necked flask equipped with reflux con-
denser and a nitrogen inlet. The mixture was stirred at 75 8C E0 0.50 0.10 0.16 0
for 48 h, then 20 mL of dried acetonitrile was injected into the E1 0.50 0.10 0.16 0.25
system to reduce the viscosity of the mixture, and the obtained E2 0.50 0.10 0.16 0.50
IL solution was slowly poured into a flask containing 1.5 L of E3 0.50 0.10 0.16 0.75
ethyl acetate. The system was left without stirring for 48 h to
complete phase separation. The light brown phase containing
acetonitrile and IL was then removed and washed 10 times with the working electrode of stainless steel. For the electrolytes and
ethyl acetate. Finally, the solvent was removed under vacuum to pure [DMIM]Br, the experiments were carried out at different
obtain the IL. Melting point 5 43.7 8C, obtained from differen- temperatures. The ionic conductivity was determined from
tial scanning calorimetry (DSC). The 1H-NMR (CDCl3, 200 eq. (1)
MHz, room temperature, d ppm) d 5 10.24 (s, 1 H), 7.32 l 1
r5 3 (1)
(s, 1 H), 7.27 (s, 1 H), 4.34–4.29 (t, J 5 7.4 Hz, 2 H), 4.12 A R
(s, 3 H), 1.92 (m, 2 H), 1.25 (bs, 14 H), 0.90–0.86 ppm where: r is the conductivity (S cm21), l 5 sample thickness
(t, J 5 6.3 Hz, 3 H) confirm the IL was obtained.31 (cm), A 5 sample area (cm2), and R 5 resistance (ohm)
Production of Polymer Electrolytes obtained by Nyquist plots.
The polymeric electrolytes were prepared by mixing epoxy resin The Arrhenius plots were obtained from the conductivity values at
with the IL and the mixture of the curing agent based on poly- different temperatures, it was calculated according to eq. (1). The
ether amine, according to the formulation presented in Table I. values were fitted using a linear trendline to determine the activa-
After mixing, the system was processed in the Speedmixer DAC tion energy of the ionic conduction, according to eq. (2),1,32–34
150.1 FVZ from FlackTek Inc., (S~ao Paulo, Brazil) for 5 min at  
Ea 1
3500 rotation per minute (RPM). log r5log A2 (2)
R T
The final mixture was then poured into molds with 8 mm
diameter and 2 mm thick, and curing using the following pro- where r is the conductivity, A is a constant that depends on the
tocol: 24 h at room temperature, 24 h at 120 8C, and 3 h at contact area, Ea is the activation energy, R (L atm K21 mol21)
150 8C. The electrolytes were stored under vacuum until the corresponds to the gas constant, and T (K) the temperature.
time of the tests. The cyclic voltammetry analysis was also performed on the
The necessary amounts of JD230 and JD2000 to promote the same equipment with the same electrodes, it was performed
polymerization of the electrolytes was based on the amine three cycles for each potential window. The measurements for
hydrogen equivalent wt. values of the jeffamines and according the ILs were carried out in different potential windows (60.1 to
to the epoxy equivalent weight of the DGEBA epoxy resin. 61.0 V) at room temperature, with scan rate of 10 mV s21. For
other temperatures, the analysis was performed only in the
Characterizations potential window from 20.75 to 0.75 V because the initial tests
The ILs and the electrolytes were characterized by TGA in nitro- performed have shown that this is the greatest potential window
gen atmosphere with heating rate of 10 8C min21 in the temper-
that the system was electrochemically stable. The electrolytes
ature range from 25 to 800 8C using TGA-Q50 TA instruments.
were also measured in this same way, but with stainless steel
DSC was performed in a temperature range from 250 to 100 8C (316 L) as electrodes.
with heating rate of 5 8C min21, in aluminum pan on Netzsch
DSC 204 F1 with LN2 Cooling. Furthermore, the nuclear mag- RESULTS AND DISCUSSION
netic resonance (1 H-NMR) of IL 1-Decyl-3-methylimidazolium Characteristics of ILs
bromide ([DMIM]Br) was obtained in CDCl3 on nuclear mag- The thermal stability of the ILs was measured by TGA, whose
netic resonance Spectrometer-Mercury 300 MHz. thermograms are illustrated in Figure 1. The onset of tempera-
ture degradation for the ILs CYPHOS IL 109, [BMIM]BF4 and
The impedance spectroscopy of the ILs was performed using the
[DMIM]Br corresponds to 230, 315, and 200 8C, respec-
potentiostat/galvanostat PGSTAT302N Autolab equipped with
tively. In spite of the difference in thermal stability, all ILs are
FRA32M module, connected to carbon electrodes (working elec-
thermally stable until around 150 8C, which is very useful for
trode and counter electrode, Supporting Information Figure S1)
electrolyte applications at temperature higher than room
and reference electrode made of pure silver. The measurements
temperature.
were conducted at room temperature in the frequency range
from 100 mHz to 0.5 MHz with the ac amplitude of 0.01 and 0 The ionic conductivities of the different ILs were determined by
V dc potential. The IL [DMIM]Br was heated at 50 8C until electrochemical impedance technique, whose Nyquist curves are
melt to be able to contact the electrode assembly. The electro- illustrated in Figure 2. The conductivity values were calculated
lytes were also evaluated under the same conditions, but using from eq. (1) whose values was 5.0 3 1021, 4.0 3 1021, and

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ARTICLE WILEYONLINELIBRARY.COM/APP
Figure 1. Degradation thermograms of the ILs CYPHOS IL 109,
[BMIM]BF4, and [DMIM]Br. [Color figure can be viewed at wileyonlineli-
brary.com]
3.0 S cm21 for CYPHOS IL 109, [DMIM]Br, and [BMIM]BF4,
respectively. The [BMIM]BF4 IL presents the highest conductiv-
ity, probably due to the smaller size of the cation, which con-
tributes for an increasing of the ion mobility and a higher
conductivity. As both CYPHOS 109 and [DMIM]Br contain
larger cations, the smaller ionic conductivity of the later may be
attributed to the higher nucleophilicity of the corresponding
anion, contributing for a decrease in ion mobility.
Cyclic voltammetry of each IL was obtained to investigate the
electroactivity of the ILs. Figure 3 illustrates the voltammograms
obtained in the range of 20.75 to 0.75 V. The IL [BMIM]BF4
presents peaks assigned for oxidation–reduction reactions in its
cyclic voltammetry curves and a potential window around 0.65
V, indicating lower efficiency as an electrolyte, when compared
with the other ILs. The IL CYPHOS IL 109 presents a better
result in terms of potential window (around 0.85 V), when
compared with the [BMIM]BF4. Nevertheless, the [DMIM]Br
presents the best results in terms of potential window (around
1.5 V), as shown in Figure 3. In spite of the lower thermal sta-
bility and lower ionic conductivity, the better electrochemical
result is an important parameter for the application in polymer
electrolytes and justifies the choice of this IL for the further
studies at higher temperature and to be used as electrolytes in
Figure 2. Nyquist plots of ILs. [Color figure can be viewed at wileyonline-
library.com]
45838 (4 of 8)
Figure 3. Voltammograms of ILs at room temperature. [Color figure can
be viewed at wileyonlinelibrary.com]
the rubbery epoxy system. Moreover, [DMIM]Br presents good
compatibility with epoxy resin, as it will be discussed in the
next section. No exudation of this IL was observed in the epoxy
composite, even with high amount of IL. In the case of
CYPHOS 109, the epoxy-based network containing even 20% of
IL presents a phase separation after the curing process and exu-
dation. Thus, the [DMIM]Br was chosen to produce the
electrolytes.
Electrochemical Behavior of [DMIM]Br
The electrochemical potential range or potential window for
[DMIM]Br was determined by cyclic voltammetry analysis in
different potential range and different temperatures. Figure 4
presents the corresponding voltamograms as a function of the
potential range and temperature. No evidence of oxidation–
reduction phenomenon was observed at room temperature,
regardless of the potential range [Figure 4(a)]. For measure-
ments at higher temperatures, the redox phenomenon observed
for the potential window between 21 and 1.0 V shifted and
started to occur toward lower values, indicating a reduction of
the potential window of IL at this temperature. Therefore, a
potential window between 20.75 and 0.75 V has been set for
the experiments performed at different temperatures. As
observed in Figure 4(b), no evidence of redox reactions was
observed for this IL even at temperature as high as 170 8C,
which is an interesting result for applications in electrolytes.
Furthermore, a significant increase of capacitance (measured by
the internal area of the voltamograms) was observed. The
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Figure 4. Voltamograms obtained at scan rate 10 mV s21 for the IL [DMIM]Br at room temperature (a), comparison of voltamograms obtained at
room temperature and 170 8C (b). [Color figure can be viewed at wileyonlinelibrary.com]

Figure 5. Nyquist diagrams for IL in the temperature range between 27 and 170 8C (a), and (b) high-frequency region. [Color figure can be viewed at
wileyonlinelibrary.com]

capacitance increases with temperature due to the viscosity of
the IL decrease and as a consequence the ionic mobility
improves.
A typical behavior of electrolytes was observed for [DMIM]Br,
according to the impedance spectroscopy. Figure 5 shows the
spectra obtained as a function of temperature. The IL showed a
linear behavior in low frequency region and its inclination is
sensitive to temperature.
In the high frequencies region, the presence of a semicircle is
observed. The interaction with the abscissa is associated with
the reactance, and this reflects the ionic mobility or migration
of ions between the electrodes. In the low frequency region, the
polarization phenomena in working and auxiliary electrodes are
observed. When the temperature is increased the ionic mobility
and the polarization are affected. In high frequency region, it is
observed the shift of the semicircle toward the zero of the

Figure 6. (a) Solution formed by DGEBA epoxy and [DMIM]Br (E3), (b) photographs of the electrolytes E3. All mixture (E1, E2, and E3) presented the
same visual aspects. [Color figure can be viewed at wileyonlinelibrary.com]

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Figure 7. TGA curve of electrolytes E0, E1, E2, and E3. [Color figure can
be viewed at wileyonlinelibrary.com]
Figure 8. DSC curves of E3 and pure epoxy E0. [Color figure can be
viewed at wileyonlinelibrary.com]
abscissa with temperature, indicating a reduction in the resis-
tance R. At room temperature, the IL [DMIM]Br presents lower
ionic conductivity, due to its solid state. However, [DMIM]Br
have good thermal stability and when exposed to higher tem-
peratures it became liquid and its viscosity decreases dramati-
cally which is important to improve its ionic conductivity. All
these characteristics make this IL able to be used to build a
high temperature energy device operating until 170 8C.
Figure 9. Nyquist plots for the electrolytes E1, E2, and E3 at temperatures of 50 8C (a) and 170 8C (b). [Color figure can be viewed at wileyonlinelibrary.
com]
45838 (6 of 8)
Figure 10. Arrhenius plots for [DMIM]Br and the electrolytes E1, E2, and
E3 and the respective linear fit curves. [Color figure can be viewed at
wileyonlinelibrary.com]
Electrolytes Evaluation
The development of the epoxy-based solid electrolytes was per-
formed using [DMIM]Br as the IL, because of its higher poten-
tial window, good thermal stability, and compatibility with
epoxy resin. Indeed, [DMIM]Br is completely soluble in the
epoxy system and forms transparent films as shown in Figure
6(a,b). It was not observed any phase separation or the exuda-
tion of IL in these systems.
After the addition of jeffamines the cure process begins and a
three-dimensional network starts to grow. Because of the pres-
ence of long segments of the JD2000, the thermoset polymer
presents a good flexibility and becomes less fragile or breakable
[Figure 6(b)]. It was not observed any phase separation or the
exudation of IL in these systems.
Thermal Characterization. Figure 7 illustrates the TGA profiles
of the epoxy networks as a function of the amount of IL. All
systems containing IL present a decomposition event below
200 8C, which is due to the presence of small amount of water
adsorbed in the system. The onset thermal degradation temper-
ature decreases as the amount of IL in the system increases. For
the system containing high amount of IL (E3), the degradation
temperature corresponds to 243 8C. This temperature is higher
than that observed for the pure IL (230 8C). It is important to
point out that all polymeric electrolytes are resistant to
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Table II. Correlations and Activation Energy (Ea) by the Arrhenius Curves
Electrolyte Intercept Slope R2 Ea (kJ mol21)
E1 4.62 23.91 0.9688 32.50
E2 4.55 23.49 0.9858 29.04
E3 5.11 23.46 0.9702 28.78
[DMIM]Br 2.50 21.24 0.9813 10.33
degradation at temperatures below 170 8C, suggesting that these
electrolytes are safe to use in this temperature range.
Figure 8 compares the DSC analysis of pure epoxy system (E0)
and that containing the highest amount of IL (E3). The pres-
ence of IL in the epoxy network shifted the glass transition tem-
perature toward lower values. This result confirms the
plasticizing effect of the IL and the miscibility of IL within the
epoxy matrix. Thus, this material presents greater flexibility and
mobility than pure epoxy network, and should present better
ionic mobility.
Electrochemical Characterization. The resistance of the epoxy
networks as a function of the IL content was evaluated from
impedance spectroscopy. Figure 9 shows the Nyquist plots for
the electrolytes. The sample E0 (without IL) was not shown in
this figure for the sake of clarity. However, the conductivity of
the sample E0 was in the order of 10211 S cm21. As expected,
the increase in IL concentration contributes to a significant
decrease in the resistance of the electrolyte. The electrolyte E3
presents the best response in terms of resistance even at low
temperatures. Furthermore, despite the large amount of IL used,
no exudation during the tests was observed, justifying its use as
electrolyte for high temperature applications.
The presence of a semicircle in the Nyquist plot is due to the
equivalent circuit that describe the electrolyte in an impedance
measurement. This circuit present some resistance and capacitor
components that are correlated with features of the electrolyte,
as the ionic mobility, for example. The scope of this article does
not include the discussion of equivalent circuit and for the pur-
pose of this work only the resistance at low frequency was ana-
lyzed since it is correlated with the ionic mobility consequently
with electrolyte conductivity.30
Figure 11. Voltamograms for electrolyte E3 at 27, 100, and 170 8C in the
range of potential between 20.75 and 0.75 V, obtained with scanning rate
of 0.01 V s21. [Color figure can be viewed at wileyonlinelibrary.com]
45838 (7 of 8)
The Arrhenius diagrams Figure 10 of each electrolytes in this
study were plotted and due to the linear behavior, and the lin-
ear correlations it was possible to determine the activation
energy (Ea) related with the ionic conductivity of IL and elec-
trolytes. The values of the angular and intercepts, as well as the
R2 value are shown in Table II. The slope was used to calculate
the activation energy of ionic conductivity.
The conductivity of the electrolyte increases linearly with tem-
perature for all specimens. Moreover, an increase in conductiv-
ity is observed as the amount of IL in the sample increased, as
expected. At high temperature, a conductivity in the range of
1025 to 1023 S cm21 was observed, which can be considered
appropriate for various applications such as solid electrolytes in
a supercapacitor. E3 was the electrolyte that exhibits the best
conductivity values and therefore would be the most suitable to
be used to produce electrochemical devices.
The cyclic voltammetry was held with the purpose of investigat-
ing the influence of the epoxy matrix on the work potential of
the electrolyte. Figure 11 shows the voltamograms obtained for
the electrolyte at 27, 100, and 170 8C, in the range of potential
from 20.75 to 0.75 V for E3.
The internal area of each voltamograms increases with tempera-
ture, indicating a large increase of the capacitance of the elec-
trode. The free volume of the matrix increase with the
temperature and the ionic mobility increase as well. The elec-
trode was made up of parallel metal plates with the same diam-
eter of electrolytes and an identical surface area. The
capacitance values obtained for even a small surface area of the
electrode indicate that the electrolyte has great potential to be
used as supercapacitors with other electrodes with larger surface
areas, for example with carbon conductive materials such as
carbon nanotubes, graphite, graphenes, and even carbon
black.35
CONCLUSIONS
In this work, a solid and flexible electrolyte constituted by
epoxy matrix loaded with high amount of IL [DMIM]Br was
reported. These electrolytes are stable even at temperature as
high as 170 8C, with no exudation of the IL. Moreover, the elec-
trolyte containing 50 wt % of IL presents conductivity around
1026 S cm21 at room temperature which increases up to 1023
S cm21 at 170 8C. Such electrolytes display potential application
on the development of electrochemical devices to be employed
at higher temperatures.
ACKNOWLEDGMENTS
This work was sponsored by Conselho Nacional de Desenvolvi-
mento Cientıfico e Tecnol
ogico—CNPq (Grant number 303457/
2013-9) and Fundaç~ao de Amparo a Pesquisa do Estado do Rio de
Janeiro—FAPERJ (grant number E-26/201.183/2014).
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