J Mater Sci (2018) 53:15784–15794

Chemical
C H E M I C A L R routes
O U T E S T Oto
M Amaterials
T E R I AL S

Surface attachment of protonated polyimidazolium

monolayer on titanate nanotubes as a novel proton
conductor
Fangfang Zhang1 , Wei Li2,* , Xi Zheng3 , Pengfei Fang1,* , and Haining Zhang3

1
School of Physics and Technology, Wuhan University, Wuhan 430072, China
2
College of Light Industry and Food Engineering, Guangxi University, Nanning 530004, China
3
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology,
Wuhan 430070, China

Received: 16 March 2018 ABSTRACT

Accepted: 24 July 2018
Published online:
30 July 2018
Ó Springer Science+Business
Media, LLC, part of Springer
Nature 2018
A novel proton conductor has been designed by the surface immobilization of
protonated polyimidazolium monolayer on titanate nanotubes (TiNTs) through
a polymer brush strategy. 2,20 -Azobis(2-methylpropionitrile) (AIBN)-type ini-
tiators are first attached to TiNTs followed by a free radical polymerization of
protonated 1-vinylimidazole (VyImBF4) on the surface. The chemical structure
of the resulting poly(VyImBF4)-modified TiNTs is verified by Fourier transform
infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). TGA curve indi-
cates their good thermal stability. The maximum proton conductivity achieves
6.74 9 10-4 S cm-1 at 200 °C under dry condition and 3.60 9 10-2 S cm-1 at
120 °C under 100% humidity, respectively, when the polymerization is carried
out under a polymerization time of 3 h and an immobilized initiator concen-
tration of approximately 42.4 mmol L-1. The proposed preparation of
poly(VyImBF4)-modified TiNTs would give a new idea for the design of other
ion conductors.

Introduction solvents, leakage proof as well as good mechanical

Recently, solid polymer electrolytes (SPEs) have
attracted enormous attention for their applications
ranging from fuel cells, batteries, hybrid power
sources and supercapacitors to sensors and elec-
trochromic display devices [1–3]. They are consid-
ered as alternatives to liquid and gel electrolytes,
which benefit from the avoidance of hazardous
properties [4]. The main concern in SPEs is their low
ionic conductivity. Since the ionic conductivity of
SPEs results from the motion of dissolved ionic spe-
cies (cations and anions) in the polymeric matrix that
normally happens in the amorphous phase [5], con-
siderable efforts have been employed to increase the
volume fraction of the amorphous domain in the
system by using polymers with low Tg [6, 7], doping

Address correspondence to E-mail: weili@gxu.edu.cn; fangpf@whu.edu.cn

https://doi.org/10.1007/s10853-018-2739-9
J Mater Sci (2018) 53:15784–15794
of inorganic submicron and nano-sized fillers [8, 9],
and synthesis of organic–inorganic hybrid materials
[10, 11].
Among these strategies, the organic–inorganic
hybrid electrolytes are of great interest due to their
highly flexible structure, enhanced segmental mobil-
ity, and high thermal stability [4]. Furthermore, they
are also desirable for anhydrous applications owing
to the water retention capability of the inorganic
moieties [12]. Among various inorganic materials,
titanate nanotubes (TiNTs) with a high water reten-
tion ability and moderate proton conductivity have
been regarded as an excellent candidate for the
design of organic–inorganic hybrid electrolytes
[13, 14]. Additionally, the selected TiNTs containing
multiple hydroxyl groups could provide access to the
surface functionalization as well as the high
hydrophilicity induced by the chemisorbed water
molecules that will facilitate proton transfer, espe-
cially under elevated temperatures [15].
Furthermore, the selection of ionic conducting
moieties is of great importance. In order to achieve a
high anhydrous conductivity for the elevated-tem-
perature operation of batteries and other electro-
chemical devices, water needs to be replaced by a less
volatile solvent that can be used as a proton-trans-
porting medium in the electrolyte [16]. Hetercycles
(e.g., imidazole molecules) are amphoteric, which are
able to undergo autoprotolysis to a high degree via
the hydrogen-bond networks, leading to a high ionic
conductivity [17]. However, considering their appli-
cation as electrolyte materials, there is a challenge for
their immobilization in the system to prevent their
leakage [18, 19]. An attractive technique is polymer-
ization, where imidazole moieties are tethered to the
polymer backbones [20–24]. In this case, the immo-
bilized amount of imidazole groups can be dynami-
cally controlled by adjusting the polymerization
conditions in order to obtain a high proton
conductivity.
To combine the advantages of the organic–inor-
ganic hybrid electrolytes as well as the polymeriza-
tion strategy, herein we designed a novel proton
conductor based on the surface attachment of proto-
nated polyimidazolium monolayer on TiNTs by a
‘‘polymer brush’’ method according to our previous
work [25]. The AIBN-type initiators were first
attached to TiNTs by a silane reaction followed by the
grafting of imidazolium-based polymers
(poly(VyImBF4)) from the surface by a free radical
15785
polymerization. The chemical structure of the
resulting poly(VyImBF4)-modified TiNTs was then
identified by FTIR spectroscopy and XPS. Finally, the
thermal stability as well as the conductivity under
different conditions of the designed electrolyte was
evaluated.
Materials and methods
Materials
1-Vinylimidazole (VyIm) was purchased from Alfa
Aesar. Tetrafluoroboric acid, diethyl ether, and
ethanol were received from Sinopharm Chem.
Reagent Co., Ltd., China. All chemicals were of ana-
lytical grade and used as received. Water was
deionized through a Milli-Q system (Barnsted
Nanopore) with a resistivity of 18.0 XM cm-1. Tita-
nium dioxide powder (P25) was purchased from
Evonik Degussa, Germany. TiNTs were prepared by
a hydrothermal method, and the detailed synthetic
procedure was reported elsewhere [15]. The AIBN-
type initiator, dimethylchloro-silylpropyl 4-isobuty-
ronitrile-4-cyano pentanoate, was synthesized
according to the literatures [26, 27].
Synthesis of imidazolium monomer
According to the literature [28], 1-vinylimidazole
(VyIm) aqueous solution (30.0 mL, 0.106 mol) was
added dropwise into tetrafluoroboric acid (HBF4,
17.7 mL, 8.2 N) in a three-neck flask under an ice-
water bath. After reaction for 12 h, the mixture was
dropped into a glass disk and dried at 40 °C under
vacuum overnight to evaporate water in solution.
Subsequently, diethyl ether (300 mL) was added into
the above solution in order to get rid of the unreacted
VyIm followed by drying at room temperature for
24 h. The resulting vinylimidazolium tetrafluoroboric
acid (VyImBF4) was identified by 1H NMR spec-
troscopy and stored in the fridge for further usage.
Preparation of polyimidazolium conductor
based on a ‘‘polymer brush’’ method
The AIBN-type initiators were first immobilized onto
TiNTs according to our previous work [25]. After
attachment, the initiator-modified TiNTs (1 g) were
suspended in an ethanol solution of VyImBF4 with a
15786
certain concentration in a Schlenk flask under N2
condition. The mixture was then degassed by five
freeze–pump–thaw cycles and polymerized at 70 °C
for a defined time. After polymerization, samples
were obtained by centrifugation and washed with
distilled water for three times. The resulting white
powders were finally dried at 60 °C under vacuum
overnight and stored in the desiccator before usage.
Therefore, the protonated polyimidazolium was
grafted from TiNTs [26], and the according prepara-
tion procedure is schematically illustrated in Fig. 1.
Characterization
1
H NMR spectroscopy was performed by a 300-MHz
Varian spectrometer (Mercury VX-300). Transmission
electron microscopy (TEM) images were taken by
first dispersing fine solid particles into ethanol and
sonicating for 30 min at room temperature. Before
Figure 1 Schematic
illustration of the preparation
of poly(VyImBF4)-modified
TiNTs.
J Mater Sci (2018) 53:15784–15794
microscopic examination, a drop of the above sus-
pension was placed on a thin carbon film supported
by a copper grid and dried under a UV lamp. TEM
images were finally obtained by a high-resolution
electron microscope (JEM-2010FEF). X-ray diffraction
(XRD) measurements were taken on a D/MaxRB
X-ray diffractometer (Rigaku, Japan) by using Cu Ka
radiation operating at 40 kV and 30 mA. Surface
area, pore volume, and pore size distribution was
calculated from the N2 adsorption–desorption iso-
therm measured at 77 K on JW-BK instrument (JWGB
Sci & Tech Co., Ltd., China). Elemental analysis was
conducted on Vario EL III analyzer (Germany).
Fourier transform infrared (FTIR) spectra were
recorded by a FTIR spectroscopy (Bio-Rad FTS 300)
with a resolution of 4 cm-1. X-ray photoelectron
spectroscopy (XPS) measurements were taken on VG
Multilab 2000 by monochromatic Mg Ka radiation
(E = 1253.6 eV) collecting up to 200 scans.
J Mater Sci (2018) 53:15784–15794
Thermogravimetric analysis (TGA) was carried out
by using the NETZSCHSTA449 C Jupiter thermal
analyzer at a heating rate of 10 °C min-1 over a
temperature range of 25–900 °C under N2 atmo-
sphere with a flow rate of 10 mL min-1. As for pro-
ton conductivity measurements, samples were first
compacted to a pellet under a pressure of approxi-
mately 20 MPa and the obtained pellet was sand-
wiched between two gold electrodes. The
measurements were then taken on an impedance
analyzer (Autolab FG30/FRA, Eco Chemie) in the
frequency range of 10 Hz and 100 kHz with the sig-
nal amplitude of 10 mV using a homemade testing
chamber under a controllable temperature and rela-
tive humidity. The resistance (R) of the compacted
pellet was estimated from Cole–Cole plots, and the
proton conductivity (r) was calculated by using the
thickness (L) of the pellet and the electrode area (S)
according to the following equation:
L tion–desorption isotherm. The calculated pore size of
r¼ ð1Þ
RS
Results and discussion
Chemical structure of VyImBF4
After the synthesis of VyImBF4, its structure was
identified by NMR spectroscopy. Figure 2 shows the
1 dispersed in ethanol without precipitation, and this
H NMR spectra of VyIm and VyImBF4. The peaks
located at 2.50 and 3.50 ppm are ascribed to the sig-
nals of DMSO-d6. As for VyIm (Fig. 2a), the chemical
shift located at 4.85 * 5.51, 7.01, 7.13 * 7.18, 7.60
and 7.95 ppm is attributed to the vinyl group (=CH2
and -CH=) and the methylene groups in the imida-
zole ring (C-4, C-3 and C-5), respectively [28]. After
neutralization, all the peaks shift to a low field as
shown in Fig. 2b. In particular, the chemical shift of
the methylene group in the C-5 position moves from
7.95 to 9.33 ppm. Interestingly, there is a weak and
wide peak at around 4.00 ppm, which could be the
signal of the protonated amine group in the imida-
zole ring. All the results indicate the successful syn-
thesis of the VyImBF4 compound.
15787
Morphology, crystal structure, and pore
properties of TiNTs
TiNTs were prepared by a hydrothermal method,
and their morphology was investigated by TEM. As
shown in Fig. 3a and b, the synthesized TiNTs have a
length of approximately 100 nm with an approximate
inner diameter of 8 nm and wall thickness of 1.4 nm.
Meanwhile, their crystal structure was evaluated by
XRD measurement, and the according XRD pattern is
displayed in Fig. 3c. The peaks located at 2h of 10.57°,
24.32° and 48.38° are ascribed to the (200), (110), and
(020) diffractions of the structure of hydrogen titanate
(H2Ti3O7), respectively [15]. This indicates a large
amount of hydroxyl groups on the surface of the
resulting TiNTs, which would be beneficial to the
surface modification. Additionally, Fig. 3d demon-
strates the pore volume and pore size distribution of
the prepared TiNTs calculated from the N2 adsorp-
the generated TiNTs is approximately 14.9 nm,
which is a little bigger than that evaluated by the
TEM measurement. This phenomenon could be due
to the limited area of the obtained TEM image. Fur-
thermore, the calculated Brunauer–Emmett–Teller
(BET) surface area of the TiNTs is about 321.1 m2 g-1.
Such high surface area could enhance water reten-
tion, which will be beneficial to the proton conduc-
tion. Meanwhile, the prepared TiNTs can be well
will be desirable for the following immobilization of
initiators.
Grafting density of initiator-attached TiNTs
The AIBN-type initiators were attached to the surface
of TiNTs by a silane reaction, and the corresponding
grafting density was investigated by elemental anal-
ysis. According to the obtained nitrogen content, the
grafting density (d, mol g-1) could be calculated by
the following equation:
gE
d¼ ð2Þ
ME  Z
where gE is the content of nitrogen element, ME is the
relative atomic mass of nitrogen element, and Z is the
number of nitrogen element in the sample. Herein,
various initiator concentrations were applied for
surface modification, and the measured content of
nitrogen element as well as the calculated grafting
15788
Figure 2 1H NMR spectra of
VyIm (a) and VyImBF4 (b) in
DMSO-d6.
density in the corresponding samples is shown in
Table 1. It can be seen that the grafting density nearly
levels off when the initiator concentration reaches
11 mmol L-1. Since the higher the grafting density of
the attached initiators is, the more grafted polymers
can be achieved in the following polymerization of
VyImBF4. This will further result in a higher density
of attached imidazole moieties, which would be
desirable for the ion conducting. Therefore, the opti-
mal initiator concentration with a value of 11 mmol
L-1 was chosen for further polymerization, and the
corresponding grafting density of initiators is
423.6 lmol g-1.
J Mater Sci (2018) 53:15784–15794
Chemical structure of poly(VyImBF4)-
modified TiNTs
Under the optimal grafting density of initiator-at-
tached TiNTs, the synthesized VyImBF4 monomers
were then polymerized and grafted from the modi-
fied TiNTs by in situ free radical polymerization.
FTIR measurement was applied to identify the
chemical composition of poly(VyImBF4)-modified
TiNTs, and the corresponding spectrum is displayed
in Fig. 4. For comparison, spectra of pure TiNTs as
well as initiator-attached TiNTs are also plotted in the
same figure. As for pure TiNTs, the absorption bands
at 3421 and 1632 cm-1 are attributed to the hydroxyl
groups on the surface, and the stretching vibration of
Ti–O–Ti bond is clearly observed at 477 cm-1 [29]. In
the spectrum of initiator-attached TiNTs, the
J Mater Sci (2018) 53:15784–15794 15789

Figure 3 a, b TEM images of

TiNTs prepared by a
hydrothermal method; c XRD
pattern of the prepared TiNTs;
and d pore volume and pore
size distribution of the
prepared TiNTs calculated
from the N2 adsorption–
desorption isotherm.

Table 1 Content of nitrogen element measured by elemental analysis and the calculated grafting density of initiator-attached TiNTs at
various initiator concentrations

Initiator concentration (mmol L-1) Content of nitrogen element (gE, %) Grafting density (d, lmol g-1)

0.5 0.587 104.8

2.8 0.794 141.8
5.5 1.213 216.6
11 2.372 423.6
13 2.398 428.2

emerged absorption band of the ester group at
1732 cm-1 indicates the successful immobilization of
the initiator molecules [26]. After the further grafting
of poly(VyImBF4), B-F stretching vibration band
emerges at 1058 cm-1 [30]. The stretching vibration
bands of unsaturated methylene groups in the imi-
dazole rings and the methylene as well as methyl
groups in the polymer backbones appear at 3142,
2932 and 2878 cm-1, respectively. The signals at 1560,
1465, and 1347 cm-1 are ascribed to the stretching
vibration of the protonated amine groups, the skele-
ton stretching vibration of the imidazole rings, and
the bending vibration of the methyl groups, respec-
tively. The peaks at 1197 and 1134 cm-1 could be due
to the stretching vibration of C-N groups [2]. All
these results indicate the successful immobilization of
poly(VyImBF4) on TiNTs.
Additionally, the chemical structure of
poly(VyImBF4)-modified TiNTs was also investi-
gated by XPS measurement, and the corresponding
XPS spectrum is displayed in Fig. 5. The obvious
peaks at 102, 153, 188, 287, 401, 458, 464, 531, 564, and
689 eV are assigned to Si2p, Si2s, B1s, C1s, N1s, Ti2p3/2,
Ti2p1/2, O1s, Ti2s, and F1s, respectively. This
15790
Figure 4 FTIR spectra of pure TiNTs, initiator-attached TiNTs,
and poly(VyImBF4)-modified TiNTs.
Figure 5 XPS spectrum of poly(VyImBF4)-modified TiNTs.
indicates the successful grafting of poly(VyImBF4)
from TiNTs by surface initiation, which is consistent
with the FTIR results.
Morphology and pore properties
of poly(VyImBF4)-modified TiNTs
The morphology of poly(VyImBF4)-modified TiNTs
was observed by TEM, and the according image is
shown in Fig. 6a. It can be seen that the nanotube
structure does not change after the attachment of
poly(VyImBF4). However, it is still difficult to deter-
mine whether there is a polymer monolayer or not
just from the TEM image. However, according to the
literature [26], the polymer monolayer grafted on the
surface of nanostructured metal oxide was generally
realized according to the polymer formation
J Mater Sci (2018) 53:15784–15794
mechanism in the ‘‘grafting from’’ technique. Fur-
thermore, their pore properties were investigated by
N2 adsorption–desorption isotherm measurement,
and Fig. 6b displays the corresponding pore volume
and pore size distribution. Accordingly, the calcu-
lated BET surface area is about 102.3 m2 g-1. The
decreased surface area compared with that of the
pure TiNTs suggests the successful immobilization of
poly(VyImBF4) on TiNTs. Meanwhile, the
poly(VyImBF4)-modified TiNTs has a pore size of
approximately 16.9 nm, which is similar to that of the
pure TiNTs. This result may indicate the successful
attachment of poly(VyImBF4) on the outer surface of
the synthesized TiNTs, which is consistent with our
previous research [31].
Thermal stability of poly(VyImBF4)-
modified TiNTs
Thermal stability is a key performance for the prac-
tical applications of the elevated-temperature proton
conductors. Figure 7 shows the TGA curves of pure
TiNTs and poly(VyImBF4)-modified TiNTs. The
weight loss below 100 °C in both samples is due to
the evaporation of free water and organic solvents
that are physically absorbed in the system. The
weight loss from 100 °C to approximately 250 °C (for
the pure TiNTs) or 300 °C (for the poly(VyImBF4)-
modified TiNTs) can be assigned to the decomposi-
tion of bound water and small molecule groups from
the grafted poly(VyImBF4); the mass loss (about 7%)
in the pure TiNTs in this temperature range indicates
their good ability of water retention, which will be
beneficial to the proton conducting. As for the
poly(VyImBF4)-modified TiNTs, the sharp weight
loss from about 300 to 550 °C could result from the
decomposition of the polymer backbone of the
immobilized poly(VyImBF4). Furthermore, there is a
less residual weight in the poly(VyImBF4)-modified
TiNTs compared with the pure TiNTs. All these
results indicate the successful attachment of
poly(VyImBF4) on TiNTs, and the generated
poly(VyImBF4)-modified TiNTs shows a good ther-
mal stability up to approximately 300 °C, which will
be desirable for their anhydrous applications.
J Mater Sci (2018) 53:15784–15794
Figure 6 a TEM image of
poly(VyImBF4)-modified
TiNTs and b pore volume and
pore size distribution of
poly(VyImBF4)-modified
TiNTs calculated from the N2
adsorption–desorption
isotherm.
Figure 7 TGA curves of pure TiNTs and poly(VyImBF4)-mod-
ified TiNTs.
Proton conductivity of poly(VyImBF4)-
modified TiNTs
Proton conductivity of poly(VyImBF4)-modified
TiNTs was finally measured under different condi-
tions by electrochemical impedance spectroscopy. As
the designed ion conductor was synthesized by sur-
face-initiated free radical polymerization, the poly-
merization conditions including the polymerization
time and the immobilized initiator concentration
would affect the molecular properties of the attached
polymers, e.g., grafting density and molecular
weight, which will further have an impact on the
proton conductivity. Figure 8a shows the proton
conductivity of poly(VyImBF4)-modified TiNTs pre-
pared by different polymerization time at a constant
immobilized initiator concentration (42.4 mmol L-1)
as a function of temperature under dry condition.
The conductivity increases with the increment of
temperature, which could be explained by the fact
that a higher temperature will enhance the molecular
movement in the polymers and further lead to an
15791
acceleration of the proton conduction. When the
temperature keeps constant, the conductivity
decreases after an initial increase with the prolonga-
tion of the polymerization time. In the beginning, the
grafting density of polymers onto TiNTs increases,
which would shorten the conducting distance and
further enhance the conductivity. However, addi-
tional increase in the polymerization time might lead
to the increase in viscosity in the system, and this
phenomenon will decrease the movement of molec-
ular chains and further result in a deceleration of
proton conducting. Moreover, the decrease in con-
ductivity above 160 °C in the sample prepared by
polymerization for 1 h could be ascribed to the fact
that the increase in conductivity from the grafted
poly(VyImBF4) with a low grafting density cannot
compensate the conductivity loss from the evapora-
tion of bound water in the system. The maximum
conductivity of the prepared electrolyte achieves
6.74 9 10-4 S cm-1 at 200 °C when the polymeriza-
tion time is 3 h.
The proton conductivity of such materials under
humid condition is also interesting to know since the
working of proton exchange membrane fuel cell will
generate water. Figure 8b demonstrates the proton
conductivity of poly(VyImBF4)-modified TiNTs pre-
pared by different polymerization time at a constant
immobilized initiator concentration (42.4 mmol L-1)
as a function of temperature under 100% humidity.
The conductivity achieves 1.60 9 10-3 S cm-1 even
under the temperature of 40 °C, which is higher than
that of samples under dry condition. When the con-
dition is dry, the attached polymer chains are coiled
with each other, and the proton transport is con-
trolled by the proton diffusion in the system. How-
ever, under humid condition, the polymer brush
15792
Figure 8 Proton conductivity of poly(VyImBF4)-modified TiNTs prepared by different polymerization time at a constant immobilized
initiator concentration (42.4 mmol L-1) as a function of temperature under dry condition (a) and 100% humidity (b).
(poly(VyImBF4)) will be stretched due to its hydro-
scopic property [32]. If the distance of the nearby
protonated imidazole moieties is close enough, the
proton transport will be expected to follow the hop-
ping mechanism; otherwise, water will act as ‘‘proton
carrier’’ for the proton transfer in the system, which
follows the vehicle mechanism. Both factors will
facilitate the proton conducting under humid condi-
tion. The highest conductivity of the prepared elec-
trolyte reaches 3.60 9 10-2 S cm-1 under 100%
humidity at 120 °C with a polymerization time of 3 h.
This result also indicates the optimal polymerization
time for poly(VyImBF4)-modified TiNTs is 3 h, which
will be applied for the further research on the effect
of the immobilized initiator concentration on the
proton conductivity.
In the following, the proton conductivity of
poly(VyImBF4)-modified TiNTs with various immo-
bilized initiator concentrations at a polymerization
time of 3 h was discussed and the according results
are shown in Fig. 9. According to Fig. 9, when the
temperature keeps constant, the proton conductivity
of poly(VyImBF4)-modified TiNTs decreases with an
initial increase as the immobilized initiator concen-
tration decreases. This phenomenon could be attrib-
uted to the fact that when the monomer concentration
and the polymerization time keep stable, the molec-
ular weight of the attached polymers will increase
with the decrease in initiator concentration. This
would lead to the increase in the amount of imidazole
moieties and further decrease the hopping distance
for proton conducting. Further increase in the poly-
mer molecular weight by the additional decrease in
immobilized initiator concentration will result in the
J Mater Sci (2018) 53:15784–15794
increase in viscosity and the inter-twist of polymer
chains in the system, which would restrict the
molecular movement and further lead to the decrease
in conductivity. When the immobilized initiator
concentration is 42.4 mmol L-1, the sample shows the
maximum conductivity with a value of 6.74 9 10-4 S
cm-1 at 200 °C under dry condition (Fig. 9a) and
3.60 9 10-2 S cm-1 at 120 °C under 100% humidity
(Fig. 9b), respectively. The obtained anhydrous con-
ductivity here is almost consistent with that of poly-
styrene with imidazole terminated flexible side
chains (7 9 10-4 S cm-1 at 200 °C in the absence of
water) [33]. Further enhancement of the proton con-
ductivity of poly(VyImBF4)-immobilized TiNTs
could be by means of increasing the flexible spacers
between the imidazole moieties and the polymer
backbone to facilitate their molecular movement [34].
Conclusion
A novel proton conductor was designed by the
immobilization of imidazolium-based polymers onto
TiNTs through a surface-initiated free radical poly-
merization strategy. The resulting poly(VyImBF4)-
modified TiNTs shows a good thermal stability up to
approximately 300 °C. The maximum conductivity
achieves 6.74 9 10-4 S cm-1 at 200 °C under dry
condition and 3.60 9 10-2 S cm-1 at 120 °C under
100% humidity, respectively, when the polymeriza-
tion was carried out under a polymerization time of
3 h and an immobilized initiator concentration of
42.4 mmol L-1. When the polymerization time
increases or the immobilized initiator concentration
J Mater Sci (2018) 53:15784–15794
Figure 9 Proton conductivity of poly(VyImBF4)-modified TiNTs with various immobilized initiator concentration at a polymerization
time of 3 h as a function of temperature under dry condition (a) and 100% humidity(b).
decreases, the conductivity decreases with an initial
increase. This phenomenon could be explained by the
fact that the increase in polymerization time would
increase the grafting density of polymers, and the
decrease in immobilized initiator concentration
would lead to a higher molecular weight of the
grafted polymers, which could increase the amount
of imidazole moieties that further enhance the proton
conductivity. However, additional increase in the
polymer grafting density or molecular weight will
increase the system viscosity, and this leads to the
restriction of molecular movement and further
decrease in the proton conducting. While under
humid condition, the attached polymer brushes will
be stretched for the proton hopping and water will
act as ‘‘proton carrier’’ for the vehicle transport,
leading to a higher proton conductivity compared
with that of samples under dry condition.
Such novel preparation method would be a mode
for designing other electrolytes in the electrochemical
devices, e.g., changing the ionic conducting mono-
mers for various applications in demand. Moreover,
the proposed theory on the effect of polymer prop-
erties on the proton conductivity will provide
strategies for the dynamical control of the ionic con-
ductivity of the designed electrolytes.
Acknowledgements
This work was supported by the National Science
Foundation of China [No. 21576216] and the Scientific
Research Foundation of Guangxi University [No.
XGZ170232].
15793
Compliance with ethical standards
Conflict of interest The authors declare that they
have no conflict of interest.
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