Solid State Ionics 262 (2014) 761764

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Solid State Ionics

journal homepage: www.elsevier.com/locate/ssi

Cross-linked poly(oxetane) matrix for polymer electrolyte containing

lithium ions
Hiromori Tsutsumi , Asami Suzuki
Applied Molecular Science, Graduate School of Medicine, Yamaguchi University, 2-16-1 Tokiwadai, Ube 755-8611, Japan

a r t i c l e

i n f o

Article history:
Received 17 May 2013
Received in revised form 7 September 2013
Accepted 9 September 2013
Available online 12 October 2013
Keywords:
Polymer electrolyte
Gel electrolyte
Cross-linked matrix
Poly(oxetane)
Lithium battery

a b s t r a c t
Oxetane, four-membered cyclic ether provides polymer compounds which have trimethylene oxide
(TMO, \CH2CH2CH2O\) through its ring-opening polymerization. New gel electrolyte lms with TMO and
ethylene oxide (EO, \CH2CH2O\) chains were prepared. The cross-linked polymer matrixes were prepared
from copolymerization of 3-(2-cyanethoxymethyl)-3-ethyloxetane (CMOX) and cross-linker which has oligo-EO
chain and two terminal oxetane rings coupled with the EO chain (DDOE or TDOE). The mixture of CMOX, DDOE
or TDOE, lithium salt (LiBF4 or lithium bis(triuoromethanesulfonyl)amide, LiTFSA), propylene carbonate and
photo-initiator was irradiated with a high pressure mercury lamp. The maximum conductivity in the gel lms
prepared from CMOX, TDOE and LiBF4 was 1.52 mS cm1 at 353 K. Repeatable plating and stripping processes
of lithium on a nickel electrode in the gel electrolyte were conrmed by cyclic voltammetry measurement.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Large-sized high energy storage devices, such as lithium ion secondary batteries (LIBs) are key devices for practical application of solar
and wind power sources. The large-sized LIBs should offer not only
high energy storage but also high safety and durability. Application of
polymer electrolytes to the LIBs is one of the solutions for high safety
and durability themselves. Lower conductivity at room temperature of
polymer electrolytes than liquid electrolytes has prevented their commercial application to the LIBs.
Gel electrolytes which contain liquid electrolytes in polymer matrix,
a normally cross-linked matrix, have been typically investigated by
many scientists [14]. Matrix polymers for the gel electrolytes are
poly(ethylene oxide) (PEO), poly(methyl methacrylate) (PMMA),
poly(acrylonitrile) (PAN) and poly(vinylidene uoride) (PVDF) [14].
Poly(oxetane)s which have trimethylene oxide (TMO) as their main
chain are prepared through ring-opening polymerization of oxetane, a
four-membered cyclic ether. The polymer with TMO main chain has
lower glass transition temperature. Some investigations of solid polymer electrolytes based on poly(oxetane) matrixes have been reported
with their applications [513]. Few applications of poly(oxetane) as a
matrix for gel electrolytes have been reported as far as we know [14].
In this paper we report preparation of poly(oxetane)-based gel
electrolytes from photo-initiated polymerization of oxetane derivatives
(CMOX, Fig. 1(a)) and cross-linker (DDOE or TDOE, Fig. 1(b), (c)) and

Corresponding author. Tel.: +81 836 85 9282; fax: +81 836 85 9201.
E-mail address: tsutsumi@yamaguchi-u.ac.jp (H. Tsutsumi).
0167-2738/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ssi.2013.09.049

their performance as a gel electrolyte, conductivity, polarization behavior

of a lithium electrode and plating and stripping processes of lithium in it.
2. Experimental
2.1. Chemicals
All reagents were used as received unless otherwise described.
Propylene carbonate (PC) and lithium salts, LiBF4 and lithium
bis(triuoromethanesulfonyl)amide (LiTFSA) were lithium battery
grade and used as received. Monomer (CMOX) [9,10] and crosslinker (DDOE, TDOE) [57] were prepared by the literature procedure. Their structures were conrmed by 1H- and 13C-NMR and
FTIR techniques.
2.2. Preparation of gel lms
Detailed preparation procedure of a gel electrolyte lm was mentioned in our previous paper [14]. The PC homogenous solution was prepared by mixing LiBF4 (0.04 g, 0.42 mmol), CMOX (0.25 g, 1.45 mmol),
DDOE (0.22 g, 0.75 mmol), photo initiator [15,16] (diphenyliodonium
hexauorophosphate, DPIHFP, 0.04 g, 0.08 mmol) and PC (0.18 mL,
2.10 mmol) at room temperature in the dark. The PC solution was poured
into an aluminum foil dish and irradiated with a high-pressure mercury
lamp (Optical Module X, USHIO, 7.5 J cm2) for 60 min at room temperature. The resulted lm presents as D(c-PCMOX)(LiBF4)20. This means
that the D(c-PCMOX)(LiBF4)20 contains LiBF4 (0.42 mmol, 20% of molar
amount of PC (2.1 mmol)). The molar ratio of CMOX to cross-linker
(DDOE or TDOE) was xed at 29 to 15 in this investigation.

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H. Tsutsumi, A. Suzuki / Solid State Ionics 262 (2014) 761764

Fig. 1. Structures of (a) monomer (CMOX), (b), (c) cross-linkers (DDOE and TDOE) and (d)
cross-linked poly(oxetane).

2.3. Measurements
An electrolyte lm was sandwiched with two stainless steel plates
(13 mm in diameter). Conductivity of the electrolyte lm was measured
with an LCR meter (HIOKI 3532-80 chemical impedance meter,
100 mVp p, 10100 kHz) under prescribed temperature conditions
from 293 K to 353 K. XRD patterns of the composite lms were recorded
with an X-ray diffraction meter (Ultima IV (Protectus), Rigaku, CuK,
= 0.1542 nm). Infrared spectra of samples were recorded with an
FTIR spectrophotometer (IRPresatge-21, Shimadzu). 1H- and 13C-NMR
spectra of the oxetane monomer, cross-linker, and resulted polymers
were obtained on an NMR spectrophotometer (JNM-Lambda-500, JEOL).
Electrochemical characterization of the solid polymer electrolyte
lms was performed with polarization measurements of a lithium electrode and cyclic voltammetry measurements of a nickel electrode in
poly(oxetane)-based gel electrolyte lms. Detailed cell congurations
and procedures for these electrochemical measurements were reported
in our previous papers [17]. Electrochemical measurements were
performed with a computer-controlled potentiogalvanostat (HZ-5000,
Hokuto Denko) under Ar atmosphere (dew point was at 203 K) at
333 K.

Fig. 2. Appearances of D(c-PCMOX)(LiX)30 lms, (a) X = BF4 and (b) X = TFSA.

3. Results and discussion

The electrolyte lms prepared from CMOX and cross-linker (DDOE
or TDOE) were transparent and exible. Their typical appearances are
shown in Fig. 2. XRD measurements of the electrolyte lms were
performed. The XRD results suggest that the added lithium salt into
the matrix is fully dissolved into the gel lms.
Temperature dependence of conductivity for the lithium-ion free gel
lms and the gel electrolyte lms with lithium salt prepared from
CMOX and cross-linker (DDOE or TDOE) is shown in Fig. 3. Conductivity

Fig. 3. Temperature dependence of conductivity for the lithium salt-free D(c-PCMOX) and
T(c-PCMOX) lms and the electrolyte lms D(c-PCMOX)(LiX)30 and T(c-PCMOX)(LiX)30,
X = BF4 or TFSA.

H. Tsutsumi, A. Suzuki / Solid State Ionics 262 (2014) 761764

763

Fig. 4. VTF plots of cross-linked poly(oxetane)-based gel electrolyte lms, D(cPCMOX)(LiLiBF4)30 and T(c-PCMOX)(LiLiBF4)30.

Table 1
The number of charge carriers and apparent activation energy of ion transport estimated
from VTF equation.
Gel lm

A/S K1/2 cm1

B/kJ mol1

D(c-PCMOX)(LiX)n

BF4

20
30
20
30
40
20
30
20
30
35

0.0735
1.07
0.188
1.94
1.58
0.944
5.63
0.454
9.03
4.52

5.80
6.14
7.03
7.48
7.74
7.35
8.19
6.63
8.86
9.39

TFSA

T(c-PCMOX)(LiX)n

BF4
TFSA

at 303 K for the lithium-ion free gel lms, D(c-PCMOX) and T(cPCMOX) lms was 17.2 S cm1 and 4.9 S cm1. This is due to
+
some amount of residual ions (PF
6 and Ar2I , Ar = benzene ring)
which were produced with photolysis of photo-initiator, DPIHFP
[15,16]. Conductivity of the D(c-PCMOX)(LiBF4)30 electrolyte was
0.476 mS cm1 at 303 K, 1.45 mS cm1 at 353 K. Conductivity of the
Fig. 6. Cyclic voltammogram of a nickel electrode in T(c-PCMOX)(LiBF4)30 electrolyte lm
at 60 C, scan rate at 1 mV s1, (a) 1st cycle and (b) from 2nd cycle to 5th cycle.

T(c-PCMOX)(LiBF4)30 electrolyte was 0.254 mS cm1 at 303 K and

1.52 mS cm1 at 353 K. As shown in Fig. 3, the temperature dependence curves of D or T(c-PCMOX) electrolyte lms are slightly convex.
The curves are best tted to an expression of the Eq. (1):
AT

Fig. 5. Polarization curves of lithium electrode in the electrolyte lms, T(c-PCMOX)(LiX)

30, X = BF4 and TFSA.

1=2

expB=RTT 0 

where is conductivity, is pre-exponential factor, which is proportional to the number of charge carriers, B is estimated activation energy
for conduction, R is gas constant, T is absolute temperature, and T0 is
normally called the equilibrium glass-transition temperature [18,19].
Fig. 4 shows typical VTF plots for the electrolyte lms, D(cPCMOX)(LiBF4)30 and T(c-PCMOX)(LiBF4)30. The plots show the linear
relationships. The VTF plots of other poly(oxetane)-based gel electrolyte lms prepared in our investigation also show the linear relationships. This indicates that viscoelastic character in the cross-linked
poly(oxetane)-based gel lms affects migration of the ions [18,19].
The estimated parameters, A and B are listed in Table 1. The estimated
activation energy values (B in Table 1) of the gel electrolytes are in the

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H. Tsutsumi, A. Suzuki / Solid State Ionics 262 (2014) 761764

range 5.80 kJ mol1 to 9.39 kJ mol1. The values are almost equal to or
lower than those of the gel electrolyte systems, PMMA-based gel electrolytes (3.33 kJ mol1 to 9.72 kJ mol1) [20], and PAN-based gel electrolytes (10.6 kJ mol1 to 14.0 kJ mol1) [21].
Electrochemical deposition and dissolution of lithium in a gel electrolyte system are key processes for application of the electrolyte to lithium
metal secondary batteries. Electrochemical responses of lithium ions in
the gel electrolytes were checked by two-type measurement, polarization measurement technique of a lithium electrode and potential
sweep of a nickel electrode in the gel electrolytes to check on the plating
and stripping processes of lithium.
Fig. 5 shows the polarization curves of a lithium electrode in the T(cPCMOX)(LiX)30 (X = BF4 or TFSA) electrolyte at 333 K. The polarization curves of lithium electrode in the gel lm gave asymmetrical
forms, which is fairly different from those observed in liquid electrolytes. Decrease in concentration of lithium ions at the lithium/gel interface under the highly cathodic polarized condition may be induced by
this phenomenon. It also suggests that the transportation rate of lithium
ions from the electrolyte bulk to the interface between an electrode and
an electrolyte lm is slower than that in liquid electrolytes.
Fig. 6 shows the cyclic voltammogram at the 1st cycle (a) and from
the 2nd to 5th cycles (b) of a nickel electrode in the T(c-PCMOX)(LiBF4)
30 electrolyte. In cathodic potential scan from ca. 3 V to 1 V increase
in cathodic current is attributed to the lithium deposition process on the
nickel electrode in the gel electrolyte. Anodic peak at 0.1 V which is due
to dissolution of the plated lithium from the nickel plate is also observed. As shown in Fig. 6(b), plating and stripping processes of lithium
on the nickel electrode are repeatable in the electrolyte lm. This observation supports the nding that the T(c-PCMOX)(LiBF4)30 electrolyte
can be used for rechargeable lithium metal secondary batteries.

has oligo-ethylene oxide units. The resulted gel electrolyte lms were
transparent, exible, and amorphous. The maximum conductivity was
1.52 mS cm1 at 353 K in the T(c-PCMOX)(LiBF4)30 gel lm. Repeatable plating and stripping processes of lithium on a nickel electrode in
the gel electrolyte were conrmed by cyclic voltammetry measurement.
The poly(oxetane)-based gel electrolyte lms are one of the candidates
as a polymer electrolyte of lithium metal secondary batteries.
Acknowledgments
This work was partially nancial supported by the Grant-in-Aid for
Scientic Research (C), KAKENHI (21560883) and the Electric Technology Research Foundation of Chugoku.
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4. Conclusion
We prepared poly(oxetane)-based gel electrolyte lms from oxetane
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