Electrochimica Acta 45 (2000) 12651270

Highly conductive polymer electrolytes prepared by in situ

polymerization of vinyl monomers in room temperature
molten salts
Akihiro Noda, Masayoshi Watanabe *
Department of Chemistry and Biotechnology, Yokohama National Uni6ersity, 79-5 Tokiwadai, Hodogaya-ku,
Yokohama 240-8501, Japan
Received 27 November 1998; received in revised form 19 April 1999
Abstract
In order to achieve highly conductive polymer electrolytes, room temperature molten salts with high ionic
conductivity have been explored, and in situ polymerization of vinyl monomers in the molten salts have been
conducted. It is found in this study that 1-ethyl-3-methylimidazolium tetrauoroborate (EMIBF
4
) and 1-butylpyri-
dinium tetrauoroborate (BPBF
4
) form room temperature molten salts, and these molten salts exhibit high ionic
conductivities of 210
2
and 310
3
S cm
1
at 30C, respectively. Certain vinyl monomers can be polymerized
in the molten salts by radical polymerization. In situ polymerization of suitable vinyl monomers gives transparent,
mechanically strong and highly conductive polymer electrolyte lms. For example, 2-hydroxyethyl methacrylate
network polymers in which BPBF
4
is dissolved exhibit an ionic conductivity of 10
3
S cm
1
at 30C. 2000 Elsevier
Science Ltd. All rights reserved.
Keywords: Polymer electrolyte; Room temperature molten salt; Ionic conductivity; 1-Ethyl-3-methylimidazolium tetrauoroborate;
1-Butylpyridinium tetrauoroborate
www.elsevier.nl/locate/electacta
1. Introduction
Conventional ion-conducting polymers, like
polyether-based polymer electrolytes, are solid solution
of electrolyte salts in polymers [15]. Ionic motion in
these polymer electrolytes is coupled with the local
segmental motion, and the increases in carrier-ion den-
sity and the mobility are inconsistent, because of the
increase in glass transition temperature (T
g
) with in-
creasing ionic concentration. These facts are reected
by the appearance of maximum ionic conductivity in
polyethers with increasing salt concentration.
On the other hand, in certain salt polymer systems,
in the range of high salt concentrations, the ionic
conductivity increases again and T
g
decreases again.
These electrolyte salts are characterized by low T
g
and
T
m
, and form supercooled liquids or molten salts with
high conductivity at room temperature. In the salt
polymer systems, so-called polymer-in-salt electrolytes
[6,7], the number of carrier ions and their mobility
increase with increasing the electrolyte concentration.
As a result, a high ionic conductivity that is not cou-
pled with the segmental motion of the polymers can be
expected to be achieved.
Certain pyridinium chlorides [810] or certain imida-
zolium chlorides [11,12] react with aluminum chloride
to form molten salts at room temperature, so-called
room temperature molten salts. The room temperature
molten salts exhibit high ionic conductivity, wide elec-
trochemical window, non-volatility, thermal stability
* Corresponding author.
0013-4686/00/$ - see front matter 2000 Elsevier Science Ltd. All rights reserved.
PII: S0013- 4686( 99) 00330- 8
A. Noda, M. Watanabe / Electrochimica Acta 45 (2000) 12651270 1266
and nonammability. The polymer-in-salt electrolytes,
which are made by dissolving compatible polymers in
the chloroaluminate molten salts, have already been
reported [6,13] to afford polymer electrolytes with high
ionic condutivity as well as rubbery electrolyte prop-
erty. However, chloroaluminate molten salts have quite
high moisture sensitivity, and the decomposed product
by hydrolysis, HCl, is highly corrosive. Recently, non-
chloroaluminate room temperature molten salts have
been explored. It is known that certain combinations of
imidazolium cations and bulky and soft anions form
ionic liquids at or near room temperature [1421].
Polymer gel electrolytes which contain non-chloroalu-
minate molten salts are also reported [22,23].
The objectives of this study are to nd new room
temperature molten salts and compatible polymers with
the molten salts for achieving highly ion-conductive
polymer-in-salt electrolytes. This paper deals with the
preparation and characterization of 1-ethyl-3-methylim-
idazolium tetrauoroborate (EMIBF
4
) and 1-butylpyri-
dinium tetrauoroborate (BPBF
4
) and with the
polymerization of vinyl monomers in the room temper-
ature molten salts in order to present a new methodol-
ogy affording highly conductive polymer electrolytes.
2. Experimental
2.1. Preparation of room temperature molten salts and
polymer electrolytes
EMIBF
4
and BPBF
4
were prepared according to
Scheme 1[17]. For EMIBF
4
, 1-ethyl-3-methylimida-
zolium chloride (EMICl) was rst prepared by the
quaternization reaction of 1-methylimidazole with
ethylchloride at 110C for 12 h in cyclohexane in an
autoclave. Crude product was puried by repetitious
recrystallization. An anion exchange reaction from
chloride to tetrauoroborate (BF
4

) was completed by
mixing equimolar quantities of EMICl and AgBF
4
, in
ethanol/water mixtures at room temperature for 12 h.
Precipitated AgCl was ltered off and obtained
EMIBF
4
was dried under reduced pressure. In the case
of BPBF
4
, 1-butylpyridinium bromide was rst pre-
pared by the quaternization reaction of pyridine with
butyl bromide at 100C for 2 days in cyclohexane, and
the post-treatments were similar to those for EMIBF
4
.
The structures of EMIBF
4
and BPBF
4
were identied
by
1
H-NMR and fast atom bombardment mass spectra.
Puried EMIBF
4
and BPBF
4
were stored in an argon
atmosphere glove box (VAC, [O
2
] B1 ppm, [H
2
O] B1
ppm).
In order to obtain polymer-in-salt electrolytes, we
tried to polymerize common vinyl monomers in
EMIBF
4
and BPBF
4
as the polymerization solvents.
Methyl methacrylate, acrylonitrile, vinyl acetate,
styrene and 2-hydroxyethyl methacrylate (HEMA) were
adopted as the vinyl monomers and were puried by
distillation. In the cases where either EMIBF
4
or
BPBF
4
and the equimolar vinyl monomers were com-
patible, radical polymerization was performed by heat-
ing the solutions at 80C for 12 h in the presence of 0.5
wt.% benzoyl peroxide as an initiator. Because of com-
paratively good compatibility of poly(HEMA) with the
molten salts in the resulting vinyl polymers, the net-
work polymer electrolytes based on HEMA and either
EMIBF
4
or BPBF
4
were prepared as follows. HEMA,
ethylene glycol dimethacrylate (EGDMA, 2 mol%
based on HEMA), and benzoyl peroxide (2 mol% based
on the monomers) as an initiator were dissolved in the
molten salts. The mixtures were spread between two
glass plates, which were separated by a 0.5 mm thick
spacer, and heated at 80C for 12 h. By this procedure,
solid polymer electrolytes with a variety of composi-
tions could be obtained.
2.2. Measurements
Differential scanning calorimetry (DSC) was mea-
sured by using a Seiko Instruments DSC 220C. The
samples for the DSC measurements were tightly sealed
in Al pans in the argon atmosphere glove box. Ther-
mograms were recorded during cooling (100 to
150C) and then heating ( 150100C) scans at a
cooling or heating rate of 10 K min
1
.
Scheme 1. Preparation procedures of EMIBF
4
and BPBF
4
.
A. Noda, M. Watanabe / Electrochimica Acta 45 (2000) 12651270 1267
Fig. 1. DSC thermograms of EMIBF
4
and BPBF
4
. Cooling
and heating rates are 10 K min
1
.
container in the glove box. For polymer electrolytes, a
lm (13 mm diameter, ca. 0.5 mm thickness) was sand-
wiched between mirror-nished stainless-steel elec-
trodes, sealed in a Teon

container, and subjected to

the impedance measurements.
Electrochemical windows of EMIBF
4
and BPBF
4
were checked by cyclic voltammetry using a three-mi-
croelectrode cell. The three-microelectrode cell consists
of a tip of a Pt wire (50 mm diameter, sealed in a glass
capillary) as a working electrode, a Pt wire (400 mm
diameter) for a counter electrode and an Ag/AgCl wire
(400 mm diameter) for a pseudo-reference electrode.
The cyclic voltammetry was performed at room temper-
ature by using a BAS 100 B/W electrochemical
workstation.
Dynamic mechanical analysis was performed under
N
2
atmosphere at 10 Hz by using a Seiko Instruments
DMS 210.
3. Results and discussion
3.1. Characterization of room temperature molten salts
Fig. 1 shows DSC thermograms of EMIBF
4
and
BPBF
4
during cooling and successive heating scans.
During cooling from 100 to 150C, neither exother-
mic nor endothermic peak could be observed except for
the heat capacity change corresponding to glass transi-
tion temperature (T
g
) for both EMIBF
4
and BPBF
4
. In
the heating scans, the thermograms showed T
g
, crystal-
lization point (T
c
) and melting point (T
m
). Their ther-
mal properties are summarized in Table 1. Since the
melting points of both of EMIBF
4
and BPBF
4
are
around 15C, we can conrm that these ionic liquids
are room temperature molten salts. Below the melting
points during the cooling scans, EMIBF
4
and BPBF
4
form supercooled liquids. We have already explored
that the crystallization rates of these molten salts are
very slow and that these supercooled liquids are fairly
stable.
Fig. 2 shows the temperature dependence of ionic
conductivity for EMIBF
4
and BPBF
4
. Both of the
Arrhenius plots of the ionic conductivity exhibit posi-
tively curved-proles, as can be expressed by WLF or
VTF equations. The ionic conductivities for EMIBF
4
and BPBF
4
are quite high and are 210
2
and 3
The ionic conductivities of EMIBF
4
and BPBF
4
were
determined by means of the complex impedance mea-
surements with stainless-steel blocking electrodes, using
a computer controlled Hewlett-Packard 4192A LF
impedance analyzer over the frequency range from 5
Hz to 13 MHz. A sample was lled between mirror-
nished stainless-steel electrodes with using a Teon

ring spacer (13 mm outer diameter, 7 mm inner diame-

ter, 2 mm thickness) and was sealed in a Teon

Table 1
Thermal properties of EMIBF
4
and BPBF
4
T
m
(C) T
g
(C) DH
m
(J g
1
) DS
m
(J deg
1
g
1
) T
c
(C) DH
c
(J g
1
) DS
c
(J deg
1
g
1
)
2.210
1
63.2 14.6 89.4 EMIBF
4
2.410
1
53.4 50.5
15.3 45.8 1.610
1
11.9 37.5 1.410
1
BPBF
4
66.7
A. Noda, M. Watanabe / Electrochimica Acta 45 (2000) 12651270 1268
Fig. 2. Arrhenius plots of ionic conductivity for EMIBF
4
and
BPBF
4
.
their polymers which are polymerized in EMIBF
4
and
BPBF
4
by radical polymerization. First, the compatibil-
ity of these monomers with EMIBF
4
and BPBF
4
were
checked, where equimolar amounts of EMIBF
4
or
BPBF
4
and a monomer were mixed. A circle in Table 2
means that the mixture is transparent and compatible,
and a cross means that the mixture is not compatible
and phase-separated. For example, in the case of
BPBF
4
, methylmethacrylate, acrylonitrile, vinyl acetate
and 2-hydroxyethyl methacrylate (HEMA) are compat-
ible, whereas styrene is not compatible. When a
monomer and the molten salt is compatible, radical
polymerization was performed with heating in the pres-
ence of a radical initiator. Interestingly, it was found
that these monomers were polymerized in EMIBF
4
or
BPBF
4
, except for vinyl acetate. However, most of the
resulting polymers were phase-separated from EMIBF
4
or BPBF
4
, as indicated by crosses. In the vinyl
monomers used in this study, poly(HEMA) showed
Fig. 3. Cyclic voltammograms of EMIBF
4
and BPBF
4
at room
temperature. Scan rate is 50 mV s
1
.
10
3
S cm
1
at 30C, respectively. For EMIBF
4
, the
obtained values are in good agreement with the data by
Carlin et al. [21]. The measurements were carried out
with cooling from 100 to 10C, and the samples were
thermally equilibrated at each temperature for at least 1
h before the measurements. However, we did not ob-
serve any remarkable change in the conductivities, cor-
responding to the melting transitions at ca. 15 C. The
conductivity results also support the stability of the
supercooled liquids.
The cyclic voltammetry for the room temperature
molten salts was carried out to investigate the electro-
chemically stable potential windows. Fig. 3 shows the
cyclic voltammograms of EMIBF
4
and BPBF
4
. For
EMIBF
4
, the irreversible reduction starts from ca. 2
V versus Ag/AgCl, and the irreversible oxidation ap-
pears at ca. 2 V versus Ag/AgCl. As the result, EMIBF
4
exhibits an electrochemical potential window wider
than 4 V, which agrees with the results reported by
Carlin et al. [16,17,21]. The electrochemical potential
window of BPBF
4
is narrower than that of EMIBF
4
and is ca. 3.4 V. The anodic limit does not largely differ
from that of EMIBF
4
, whereas the cathodic limit is
much higher than that of EMIBF
4
. The pyridinium
structure is more easily reduced than the imidazolium
structure. It is also interesting to note the reports by
Carlin et al. [21] statingthat EMIBF
4
is not reduced
with the addition of a trace amount of H
2
O down to
the lithium redox potential.
3.2. Preparation and ionic conducti6ity of polymer
electrolytes
Table 2 shows the compatibility of EMIBF
4
and
BPBF
4
with ve common vinyl monomers and with
A. Noda, M. Watanabe / Electrochimica Acta 45 (2000) 12651270 1269
Table 2
Compatibility
a
of EMIBF
4
and BPBF
4
with monomers
b
and their polymers
c
BPBF
4
EMIBF
4
Polymer Monomer Monomer Polymer
Methyl methacrylate
Acrylonitrile
Vinyl acetate No polymerization No polymerization
Styrene
2-Hydroxyethyl methacrylate
a
, transparent; , translucent; , phase-separated.
b
Molten salts and monomers were mixed at a 1:1 molar ratio.
c
Polymerization was carried out in the presence of 0.5 wt.% BPO at 80C for 12 h.
comparatively good compatibility and the mixtures af-
ter polymerization gave translucent gels. Thus, we at-
tempted to obtain a new solid polymer electrolyte by
using HEMA. Transparent and mechanically strong
polymer-in-salt electrolytes could be obtained by using
HEMA, ethylene glycol dimethacrylate (EGDMA) and
room temperature molten salts. By this procedure, solid
polymer electrolytes with a variety of compositions
could be obtained. The amount of unreacted monomers
after the polymerization was checked but was found to
be negligible for both of the EMIBF
4
and BPBF
4
polymer electrolytes.
Figs. 4 and 5 show the temperature dependence of
ionic conductivity for the polymer electrolytes based on
the HEMA network polymers and the room tempera-
ture molten salts. The remarkable decrease of the ionic
conductivities at the melting points of the room temper-
ature molten salts is not observed in these results. The
ionic conductivity of the EMIBF
4
electrolyte lms are
considerably lower than that of the molten salt itself
(Fig. 4). The electrolyte lms were mechanically hard,
and the phase-separation occurred at the higher compo-
sitions than [EMIBF
4
]/[Monomer] =4/6, giving translu-
cent lms. On the other hand, the compatibility of
BPBF
4
with the HEMA network polymers is rather
good, though the ionic conductivity of BPBF
4
itself is
lower than that of EMIBF
4
. The ionic conductivity of
the BPBF
4
polymer electrolytes increases with increas-
ing the concentration of BPBF
4
(Fig. 5). The ionic
conductivity of the 6/4 ([BPBF
4
]/[Monomer]) electrolyte
reaches 10
3
S cm
1
at 30C, and obtained polymer
electrolyte lm was optically compatible, transparent
and mechanically strong. Fig. 6 shows the temperature
dependence of dynamic mechanical properties for a
BPBF
4
polymer electrolyte lm ([BPBF
4
]/[Monomer] =
4/6), as a typical example. A large relaxation in tensile
modulus (E%) and a peak in tan l are observed at ca.
20C. Although this temperature is close to T
m
of
BPBF
4
, the DSC thermogram did not exhibit any melt-
ing transition at this temperature. Thus, this relaxation
temperature is assigned to T
g
of the polymer electrolyte.
This temperature is much higher than T
g
of BPBF
4
( 66.7C) and is much lower than T
g
of PHEMA
(90C), indicating the compatibility between BPBF
4
and the HEMA network polymer.
4. Conclusion
EMIBF
4
and BPBF
4
form room temperature molten
salts with melting points of ca. 15C and exhibit a high
ionic conductivity of 210
2
and 310
3
S cm
1
at
30C, respectively. Electrochemically stable potential
window of EMIBF
4
and BPBF
4
is ca. 4 and 3.4 V,
respectively. Certain vinyl monomers can be poly-
merized in the molten salts by radical polymerization. By
the radical polymerization, highly conductive solid
electrolytes based on the PHEMA network polymers, in
which molten salts are dissolved and compatible, can be
obtained.
Fig. 4. Arrhenius plots of ionic conductivity for EMIBF
4
and
their polymer-in-salt electrolytes ([EMIBF
4
]/[HEMA]).
A. Noda, M. Watanabe / Electrochimica Acta 45 (2000) 12651270 1270
Fig. 5. Arrhenius plots of ionic conductivity for BPBF
4
and
their polymer-in-salt electrolytes ([BPBF
4
]/[HEMA]).
(No. 282/10131228) from the Japanese Ministry of
Education, Science, Sports and Culture, and by NEDO
International Joint Research Grant.
References
[1] J.R. MacCallum, C.A. Vincent (Eds.), Polymer Elec-
trolyte Reviews 1 and 2, Elsevier, London, 1987, 1989.
[2] M.B. Armand, Ann. Rev. Mater. Sci. 16 (1986) 245.
[3] C.A. Vincent, Prog. Solid State Chem. 17 (1987) 145.
[4] M. Watanabe, N. Ogata, Br. Polym. J. 20 (1988) 181.
[5] M.A. Ratner, D.F. Shriver, Chem. Rev. 88 (1988) 109.
[6] (a) M. Watanabe, in: B.V.R. Chowdari, S. Chandra, S.
Singh, P.C. Srivastava (Eds.), Solid State Ionics: Materi-
als and Applications, World Scientic, Singapore, 1992,
pp. 149. (b) M. Watanabe, S. Yamada, K. Sanui, N.
Ogata, J. Chem. Soc. Chem. Commun. (1993) 929.
[7] C.A. Angell, C. Liu, E. Sanchez, Nature 362 (1993) 137.
[8] F.H. Hurley, T.P. Wier Jr., J. Electrochem. Soc. 98 (1951)
203.
[9] R.J. Gale, B. Gilbert, R.A. Osteryoung, Inorg. Chem. 17
(1978) 2728.
[10] J. Robinson, R.A. Osteryoung, J. Am. Chem. Soc. 101
(1979) 323.
[11] J.S. Wilkes, J.A. Levisky, R.A. Wilson, C.L. Hussey,
Inorg. Chem. 21 (1982) 1263.
[12] A. Fannin Jr., D.A. Floreani, L.A. King, J.S. Landers,
B.J. Piersma, D.J. Stech, R.L. Vaughn, J.S. Wilkes, J.L.
Williams, J. Phys. Chem. 88 (1984) 2614.
[13] M. Watanabe, S. Yamada, N. Ogata, Electrochim. Acta
40 (1995) 2285.
[14] J.S. Wilkes, M.J. Zaworotko, J. Chem. Soc. Chem. Com-
mun. (1992) 965.
[15] J. Fuller, R.T. Carlin, H.C. De Long, D. Haworth, J.
Chem. Soc. Chem. Commun. (1994) 299.
[16] R.T. Carlin, H.C. De Long, J. Fuller, P.C. Trulove, J.
Electrochem. Soc. 141 (1994) L73.
[17] J. Fuller, R.A. Osteryoung, R.T. Carlin, Abstract 15, The
Electrochemical Society Meeting Abstracts, vol. 95-1,
Reno, NV, May 2126, 1995, pp. 27.
[18] V.R. Koch, C. Nanjundiah, G.B. Appetecchi, B. Scrosati,
J. Electrochem. Soc. 142 (1995) L116.
[19] V.R. Koch, L.A. Dominey, C. Nanjundiah, J. Elec-
trochem. Soc. 143 (1996) 798.
[20] P. Bonhote, A.-P. Dias, N. Papageorgiou, K. Kalyana-
sundaram, M. Gratzel, Inorg. Chem. 35 (1996) 1168.
[21] J. Fuller, R.T. Carlin, R.A. Osteryoung, J. Electrochem.
Soc. 144 (1997) 3881.
[22] J. Fuller, A.C. Breda, R.T. Carlin, J. Electrochem. Soc.
144 (1997) L67.
[23] J. Fuller, A.C. Breda, R.T. Carlin, J. Electroanal. Chem.
459 (1998) 29.
Fig. 6. Temperature dependence of E% and tan l for HEMA
network polymers with dissolved BPBF
4
([BPBF
4
]/
[Monomer] =4/6).
Acknowledgements
This research was supported in part by Grant-in-Aid
for Scientic Research (No. 10650878) and that on
Priority Area Electrochemistry of Ordered Interfaces
.