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Journal of Membrane Science 518 (2016) 243–253

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Journal of Membrane Science


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

Enhanced proton conductivity of Nafion nanohybrid membrane


incorporated with phosphonic acid functionalized graphene oxide at
elevated temperature and low humidity
Bei Zhang a,b, Ying Cao a,b, Shengtao Jiang c, Zhen Li a,b, Guangwei He a,b, Hong Wu a,b,d,n
a
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China
b
Key Laboratory for Green Chemical Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
c
College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China
d
Tianjin Key Laboratory of Membrane Science and Desalination Technology, Tianjin University, Tianjin 300072, China

art ic l e i nf o a b s t r a c t

Article history: Nafion-based nanohybrid membranes doped with phosphonic acid-functionalized graphene oxide (PGO)
Received 31 December 2015 are fabricated for an ideal prospect in the application of proton exchange membrane fuel cells (PEMFCs).
Received in revised form Graphene oxide (GO) is synthesized with a modified Hummers method and coated with polydopamine
1 July 2016
via the self-polymerization of dopamine, followed by grafting with alendronic acid through Micheal
Accepted 14 July 2016
Available online 16 July 2016
addition reaction. This method enables abundant phosphonic acid groups to be grafted on the GO na-
nosheets. The incorporation of such phosphonic acid-functionalized graphene (PGO) into Nafion matrix
Keywords: generates additional proton-conducting sites and improves the water adsorption and retention capacity
Phosphonic acid of nanohybrid membranes. More importantly, the distribution of phosphonic acid groups in membrane is
Graphene oxide
controlled by the unique structure of GO nanosheets, which benefits the formation of new pathways for
Nafion
proton hopping at low humidity conditions. Consequently, the nanohybrid membranes show improved
Nanohybrid membrane
Proton conductivity proton conducting capacity, especially under high temperature or low relative humidity. The nanohybrid
membrane with 2 wt% PGO exhibits a proton conductivity of 0.277 S cm  1 at 100 °C and 100% RH, and
0.0441 S cm  1 at 80 °C and 40% RH, which are 1.2 and 6.6 times higher than that of pristine Nafion
membrane. Meanwhile, the Nafion/PGO-2.0 membrane displays the best fuel cell performance with the
highest power density of 213.12 mW cm  2 and open circuit voltage of 0.939 V.
& 2016 Elsevier B.V. All rights reserved.

1. Introduction 100% relative humidity (RH) [1]. Nevertheless, the proton con-
s
ductivity of Nafion membrane depends critically on the presence
Proton exchange membrane fuel cells (PEMFCs) are regarded as of water. At elevated temperature or low RH, a sharp decline of
s
promising power sources due to their attractive features such as proton conductivity is observed for Nafion membrane due to its
high power density, simple modular design, high efficiency and dehydration [4,5]. Currently, the following two approaches are
rapid start up [1]. As the core components of PEMFCs, proton ex- usually used to improve the membrane conductivity at low RH and
change membranes (PEMs) have attracted extensive attention, elevated temperatures by incorporating hydrophilic inorganic ad-
s
especially on membrane materials. Nafion series membranes ditives into Nafion to improve its water retention capacity [6–10]
or by introducing specific water-independent proton-conducting
commercialized by DuPont Co. are the representatives of the cur-
s groups to conduct protons without the aid of water [11] such as
rent state-of-art PEMs. Nafion series membranes are a kind of
phosphonic acid, imidazole, butyl methyl imidazolium triflate, etc.
perfluorosulfonic acid ionomer membrane composing of hydro-
[12–15].
phobic poly-(tetra-fluoroethylene)-like backbone and hydrophilic Graphene oxide (GO) is an important kind of derivative of
pendant side chains with terminated sulfonic groups [2,3]. The graphene. GO is considered as an amphiphilic material with hy-
s
unique structure endows Nafion membranes with not only good drophilic regions containing oxygenic groups (such as carboxylic,
chemical stability but also desirable proton conductivity under hydroxyl, and epoxy groups) and hydrophobic regions composed
of sp2 graphite [16,17]. GO is used as an attractive inorganic ad-
n
Correspondence to: School of Chemical Engineering and Technology, Tianjin
ditive for hybrid membranes for its unique two-dimensional
University, Tianjin 300072, China. structure and high surface area [18,19]. It has been reported that
E-mail address: wuhong@tju.edu.cn (H. Wu). the incorporation of GO can adjust proton conductivity by

http://dx.doi.org/10.1016/j.memsci.2016.07.032
0376-7388/& 2016 Elsevier B.V. All rights reserved.
244 B. Zhang et al. / Journal of Membrane Science 518 (2016) 243–253

endowing the membrane with enhanced hydrophilic property and To prepare the PGO, 30 mg of dopamine and 30 mg of GO were
controlling the state of water confined in ionic channels in the dispersed in 150 mL of 0.01 mol L  1 Tris-Cl solution (pH ¼8.5) and
polymer matrix [20–22]. Moreover, GO is a good proton conductor treated by sonication in an ice-water bath for 10 min. The mixture
after modified with proton conductive groups in its interlayer was stirred continuously at 30 °C. After 24 h, the polydopamine
space [21,23,24]. The modification of GO is mostly realized via modified GO (DGO) was separated by centrifugation. Subse-
chemical reactions between modifiers and oxygenic groups on GO quently, 49 mg of alendronic acid was added into DGO solution.
[23]. So far, sulfonic acid-functionalized GO are intensively studied The mixed solution was stirred at 30 °C for 24 h. Then the product
as fillers in hybrid membranes [19,25,26], whereas few efforts was collected through centrifugation and washed until neutral pH.
have been dedicated to other proton conducting groups owing to Finally, the prepared phosphonic acid-functionalized GO (PGO)
the limitation of possible reactions. was freeze-dried and grinded into powder.
It is well known that dopamine can undergo self-polymeriza-
tion to produce an adherent polydopamine which is coated on a 2.3. Membrane preparation
wide range of substrates (eg. polymer surfaces, metal and metal
oxide) at a weak alkaline pH [27,28]. The above process is ac- Nafion-based nanohybrid membranes were prepared by the
companied by oxidizing catechol groups to form the quinone, solution casting method. First of all, a certain amount of PGO was
which can react with various functional groups via Schiff base dispersed in 4 mL of DMAc under stirring and ultrasonication for
reaction or Michael addition and form covalently functional layers 24 h. Then 0.2 g of Nafion which had been dried for 24 h under
[29,30]. Inspired by the above feature, GO surface can be further 60 °C was redissolved in the solution and stirred at 25 °C to make
modified making use of dopamine as a capping agent to obtain the solution mixed completely. The obtained casting solution was
more kinds and larger amount of proton-conducting groups. poured onto a clean flat glass plate in an oven at 80 °C for 12 h and
In this study, a novel kind of nanohybrid membrane composed heated up to 120 °C for 12 h to remove the solvent. Afterwards,
of Nafion and phosphonic acid-functionalized graphene oxide is peeled off from the glass, the nanohybrid membranes were suc-
fabricated. To increase the loading amount of phosphonic acid cessively immersed in boiling H2O2 (3 vol%), boiling deionized
groups, GO is firstly modified by dopamine, and then grafted with water, boiling H2SO4 (1 M) and deionized water respectively. The
amino-terminated alendronic acid via Michael addition reaction. resultant nanohybrid membranes were named as Nafion/PGO-X,
The resultant phosphonic acid functionalized GO (PGO) is in- where X refers to weight percentage of PGO relative to Nafion.
corporated into Nafion matrix with the aim of improving the Nafion-based nanohybrid membranes doped with GO and DGO
proton conducting property of membrane, especially at evaluated were prepared at the same time and named as Nafion/GO-X and
temperature and low RH. The as-prepared PGO and membranes Nafion/DGO-X respectively.
are characterized by TEM, SEM, XRD, TGA, XPS and FTIR. Mean-
while, the membrane property is evaluated in terms of proton 2.4. Characterizations
conductivity, water uptake, swelling degree and single fuel cell
performance. The morphology of the as-prepared GO, DGO and PGO was
observed by transmission electron microscopy (TEM, JEOL), while
their chemical composition was determined by fourier transform
2. Experimental infrared spectra (FTIR, 4000–400 cm  1). X-ray photoelectron
spectroscopy (XPS) was utilized with a PHI-1600 spectrometer
2.1. Materials using Al Kα radiation for excitation to further confirm the che-
mical composition of PGO.
5% Nafion solution was produced by Dupont and purchased Field emission scanning electron microscopy (FESEM, Nanosem
from Shanghai Hesen Scientific Co., Ltd. Tris-Cl (4 99.9%) and flake 430) was utilized to examine the microstructure of cross-sectional
graphite were supplied by Sigma-Aldrich, as well as the dopamine morphology in the as-prepared Nafion membranes. And to in-
(4 95%). Alendronic acid (498%) was purchased from TCI vestigate the nanostructure of both pristine Nafion and nanohy-
(Shanghai) Development Co., Ltd. Hydrogen peroxide (H2O2, 30%), brid membranes, X-ray diffraction scattering (XRD) was used with
potassium permanganate (KMnO4), sodium nitrate (NaNO3), and a scanning rate of 5° min  1 with an angular range of 5–50°. Tested
dimethylacetamide (DMAc, 499.8%) were supplied by Aladdin- under the heat-up rate of 10 °C min  1, thermo gravimetric ana-
reagent. Hydrochloric acid (HCl, 36–38%) was purchased from lysis (TGA) of prepared membranes was recorded by a Perkin-El-
Guangfu Fine Chemical Research Institute (Tianjin, China), as well mer Pyris instrument to evaluate the thermal stability under N2
as concentrated sulfuric acid (H2SO4, 95–98%). atmosphere from 30 °C to 800 °C.

2.2. Synthesis of phosphonic acid-functionalized graphene (PGO)


2.5. Water uptake and swelling degree

GO was successfully prepared via a typical Hummers method


The membranes were cut into rectangular-shaped samples
using graphite powder[31]. The detailed synthetic steps were as
drying in an 80 °C oven. Each of these dried samples which had a
follows: 150 mL of concentrated sulfuric acid (H2SO4) was added
weight of Wdry (g) and an area of Adry (cm2) was soaked in room-
into a round-bottomed flask while cooled in an ice-water bath.
temperature water. 24 h later, the samples were wiped by tissue
Then 2.5 g of sodium nitrate (NaNO3) and 2 g of powdered gra-
paper. Its weight (Wwet), as well as area (Awet) were measured
phite were added with vigorous stirring and 15 g of crystal KMnO4
again at 25 °C. The water uptake as well as swelling degree of
was added in batches. The mixture was stirred at 35 °C. After
membranes can be calculated using the following equations:
30 min, a certain quantity of water was added slowly to dilute the
mixture and stirred continuously for another 30 min. When add- Wwet − Wdry
water uptake (%) = × 100%
ing more deionized water and 5% H2O2, the reaction mixture was Wdry (1)
filtered immediately. Subsequently, the oxidation product was
circularly washed with 5% HCl and water until neutral pH. Lastly, A wet − Adry
collected by centrifugation, the obtained powdered GO was dried swelling degree (%) = × 100%
Adry (2)
at 25 °C.
B. Zhang et al. / Journal of Membrane Science 518 (2016) 243–253 245

Both the water uptake and swelling degree of as-prepared 3.1. Characterization of PGO
membranes were measured three times and the average values
were calculated. The morphology and nanosheet structure of GO, DGO and PGO
were investigated by TEM as shown in Fig. 2. Single-layer GO na-
nosheets with some wrinkles are observed, consistent with the
2.6. Proton conductivity
typical morphology reported in literatures. No obvious differences
Proton conductivity was measured through the AC impedance in morphology are observed after the functionalization of dopa-
mine and subsequent phosphonic acid.
spectroscopy analyzer. When testing the function of proton con-
As displayed in Fig. 3, the chemical composition of GO, DGO
ductivity vs. temperature under 100% RH, the membranes were
and PGO was determined by FTIR. In the spectrum of GO, char-
heated with water vapor at a temperature range of 30–110 °C.
acteristic peaks at 3406 cm  1, 1724 cm  1, 1625 cm  1, 1225 cm  1
When testing the function of proton conductivity vs. RH at 80 °C,
and 1045 cm  1 correspond to O–H stretching vibration, C ¼ O
saturated salt solutions (K2CO3: RH ¼40.1%, NaNO2: RH ¼57.5%,
stretching vibration, absorbed water flexural vibration, C–O
KCl: RH ¼78.9%) were utilized to control the RH into the stainless
stretching vibration of carboxyl groups and carbon-hydroxyl (C–
steel container. To make sure that the impedance value had been
OH) stretching vibration, respectively. The appearance of these
reached constant, the membranes should be equilibrated for over
peaks confirms the successful synthesis of graphene oxide [29]. In
6 h.
the spectrum of DGO, the new peak at 1377 cm  1 corresponds to
Proton conductivity can be calculated by the following equa-
the C–O–H flexural vibration of polydopamine [28]. However, the
tion:
characteristic peaks of P ¼O and P–O of alendronic acid in the
l spectrum of PGO are not distinguished because they are over-
σ (S cm−1) =
AR (3) lapped by the peaks of GO at 1225 cm  1 and 1045 cm  1.
2 The successful grafting of phosphonic acid was examined
where A (cm ) represents the membrane area, l (cm) refers to the
through XPS. Upon analysis of overall XPS patterns displayed in
distance between two electrodes and R (Ω) refers to the mem-
Fig. 4(a), peaks attributed to O 1s, C 1s, N 1s and P 2p are observed.
brane resistance.
Upon high resolution analysis, at about 284.2 eV, 285.5 eV,
286.7 eV and 287.9 eV, the C 1s peak has been curve-fitted into
2.7. Fuel cell experiment four peak components, which is attributed to the bonding energy
of carbon in C–C, C–N, C–O and C ¼ O species, respectively (Fig. 4
The single fuel cell test was conducted at 60 °C under (b)) [27]. The C–N peak at 285.5 eV and the N 1s peak appearing at
100 mL min  1 and 150 mL min  1 flow rate of H2 and O2, respec- about 400 eV (Fig. 4(c)) further verify the successful synthesis of
tively. With an active area of 6.25 cm2, the membrane electrode DGO. The P 2p peaks at 131.5 and 132.7 eV, as well as the O 1s
assembly (MEA) was prepared through hot pressing the nanohy- peaks at 531.5 and 532.4 eV, confirm the presence of P–O and P¼ O
brid membranes with the carbon paper coating with Pt/C catalyst bonds as shown in Fig. 4(d) and Fig. 4(e) [32,33], indicating that
at 3 MPa and 165 °C for 5 min. The contents of Pt/C catalyst were the alendronic acid has been successfully grafted on the DGO
0.10 and 0.25 mg cm  2 for anode and cathode. Before the test, the surface.
fuel cell should be pre-activated for 5 h under the operating
condition. 3.2. Characterization of membranes

The distribution of DGO/PGO in Nafion matrix and the micro-


3. Results and discussion structure of as-prepared membranes were observed by SEM.
Cross-section images of Nafion and Nafion/DGO as well as Nafion/
The synthetic process of DGO and PGO is elucidated in Fig. 1 via PGO nanohybrid membranes are presented in Fig. 5. It can be
the self-polymerization of dopamine and the Michael addition. observed that DGO and PGO nanosheets are dispersed

Fig. 1. Synthetic process of DGO and PGO.


246 B. Zhang et al. / Journal of Membrane Science 518 (2016) 243–253

Fig. 2. TEM images of GO (a), DGO (b), and PGO (c).

homogeneously in Nafion matrix, and no obvious structural de-


fects are observed, indicating the good compatibility of Nafion
GO 1625 1225 1045 matrix and DGO/PGO nanosheets.
XRD measurement was carried out to examine the crystallinity
3406 of membranes and the results were shown in Fig. 6. The recast
PGO 1724 Nafion membrane displays a relatively strong and sharp peak at
the 2θ angle of 17° which is formed by the superposition of
Transmittence

amorphous peak at 16° attributed to the poly four-fluorocarbon


DGO backbone and the crystalline peak at 17.5°. Besides, a wide peak
appears at 38–39°. These results are consistent with what the lit-
erature has reported [34]. In the spectra of Nafion/GO, Nafion/DGO
and Nafion/PGO nanohybrid membranes, no new characteristic
1377 peaks are found, indicating that these nanohybrid membranes still
maintain the basic framework of Nafion. Compared with the recast
Nafion membrane, the peak at 17° of the nanohybrid membranes
is broadened and the intensity decreases due to the fact that the
4000 3500 3000 2500 2000 1500 1000 500
incorporation of GO/DGO/PGO induces the rearrangement of the
Wave Number / cm -1
phase separation structure of Nafion and thus leading to decreased
Fig. 3. FTIR spectra of GO, DGO and PGO. crystallinity. The crystallinity degree of pure Nafion and hybrid
B. Zhang et al. / Journal of Membrane Science 518 (2016) 243–253 247

O 1s 15000

12500
C 1s
10000

N 1s
c/s

c/s
7500

5000
P 2p

2500

0
1200 1000 800 600 400 200 0 275 280 285 290 295 300
Binding Energy/ eV Binding Energy / eV

5100 1300

1200
4800

1100
4500
1000
c/s

4200
c/s 900
3900
800
3600
700
3300
600
390 395 400 405 410 415 125 130 135 140 145
Binding Energy / eV Binding Energy / eV

21000

18000

15000
c/s

12000

9000

6000

3000
520 525 530 535 540 545
Binding Energy / eV

Fig. 4. Overall XPS spectra of PGO (a), XPS spectra of C 1s (b), N 1s (c), P 2p (d), O 1s (e).

membranes is estimated through peak fitting method with soft- 3.3. Thermal stability of membranes
ware and listed in Table 1. The pure Nafion membrane exhibits the
highest crystallinity degree of 34.52%, while nanohybrid mem- The thermal property of as-prepared membranes was de-
branes incorporated with GO, DGO and PGO show decreased termined through TGA as shown in Fig. 7. There are three stages of
crystallinity. The calculative results have same changing trends weight loss in TGA curves for all of the membranes. The first stage
with XRD patterns. (50–150 °C) is ascribed to the evaporation of absorbed water. The
248 B. Zhang et al. / Journal of Membrane Science 518 (2016) 243–253

Fig. 5. SEM images of the pristine Nafion membrane and nanohybrid membranes: Nafion (a), Nafion/DGO-1.0 (b), Nafion/DGO-2.0 (c), Nafion/PGO-1.0 (d), Nafion/PGO-2.0
(e).
B. Zhang et al. / Journal of Membrane Science 518 (2016) 243–253 249

Nafion/DGO-2.0

Intensity
Intensity

Nafion/GO-2.0 Nafion/DGO-1.5

Nafion/GO-1.0 Nafion/DGO-1.0

Nafion/DGO-0.5
Nafion
Nafion

0 10 20 30 40 50 0 10 20 30 40 50
2 θ / degree 2 θ / degree

Nafion/PGO-2.0
Intensity

Nafion/PGO-1.5

Nafion/PGO-1.0
Nafion/PGO-0.5
Nafion

0 10 20 30 40 50
2 θ / degree

Fig. 6. XRD spectra of recast Nafion and nanohybrid membranes: Nafion/GO (a), Nafion/DGO (b), Nafion/PGO (c).

3.4. Water uptake and swelling degree


Table 1
Crystallinity degree of the Nafion mem-
brane and nanohybrid membranes. The water uptake, as well as swelling degree were measured at
25 °C and shown in Fig. 8. The water uptake and swelling degree of
Membrane Crystallinity degree/% recast Nafion membranes are 29.17% and 30.91%, respectively.
After the incorporation of GO/DGO/PGO nanosheets, the nanohy-
Nafion 34.52 7 0.53
Nafion/GO-1.0 33.247 0.49 brid membranes show increased water uptake but decreased
Nafion/GO-2.0 32.177 0.47 swelling degree. As the loading of GO nanosheets increased, the
Nafion/DGO-0.5 32.85 7 0.23 water uptake of Nafion/GO nanohybrid membranes increases
Nafion/DGO-1.0 32.007 0.98
owing to the hydrophilic character of GO. Compared with the re-
Nafion/DGO-1.5 30.917 0.37
Nafion/DGO-2.0 29.31 70.94
cast Nafion membrane and the Nafion/GO membranes, the Nafion/
Nafion/PGO-0.5 32.88 7 0.97 PGO nanohybrid membranes exhibit the highest water uptake. The
Nafion/PGO-1.0 32.34 7 0.82 nanohybrid membrane with 1.5 wt% PGO exhibits a water uptake
Nafion/PGO-1.5 30.78 7 0.70 of 45.27%, which is about 55% higher than that of Nafion. This is
Nafion/PGO-2.0 29.05 7 0.55
because the large surface area of GO and polydopamine on its
surface enable larger phosphonic acid loading, thus further en-
hancing the water absorbing capacity of nanohybrid membranes.
second stage (250–400 °C) is attributed to the degradation of
The swelling degree is basically influenced by the following two
sulfonic acid group in Nafion and organics introduced to GO na-
factors. On one hand, the interaction between polymer matrix and
nosheets [23]. The third stage (above 400 °C) is due to the de-
inorganic fillers restrains the mobility of polymer chains and re-
composition of Nafion backbone and polydopamine. The thermal
sults in decreased swelling degree. But on the other hand, the
stability of membranes satisfies the requirements of fuel cell op- increased water uptake gives rise to more water molecules in
eration and is not affected after the incorporation of GO, DGO and hydrophilic clusters, leading to an increased swelling degree. For
PGO. all of the nanohybrid membranes, as the first reason is the
250 B. Zhang et al. / Journal of Membrane Science 518 (2016) 243–253

dominant factor, it is much lower than Nafion in terms of the


100 swelling degree. However, as more and more GO/DGO/PGO na-
nosheets are incorporated in Nafion matrix, the effect of the sec-
ond reason gradually becomes prominent, and therefore the
80
swelling degree of nanohybrid membranes increases slightly with
increasing filler content.
60
Weight /%

3.5. Proton conductivity at different temperature


40
Nafion
Nafion/GO-1.0 As a key factor of PEMs, proton conductivity is carried out to
Nafion/GO-2.0 evaluate the performance for potential use in PEMFCs. Proton
20 transfer in membranes generally follows two mechanisms: “vehi-
cular mechanism”, in which protons diffuse through the formation
of hydronium ions, and “Grotthus mechanism”, in which protons
0
are transferred through hopping among proton-conducting sites
[35,36]. Therefore, proton conductivity is mainly determined by
0 100 200 300 400 500 600 700 800 900
the following three factors: 1) the density of proton-conducting
o
Temperature/ C groups, 2) the connectivity of proton-transporting channels, and 3)
the water uptake of membranes.
The proton conductivity of Nafion and nanohybrid membranes
was tested at 100% RH. The results were shown in Fig. 9. In the
100 range of 30–110 °C, the proton conductivity of both Nafion and
nanohybrid membranes increases with temperature. Compared
with Nafion membrane, the Nafion/GO nanohybrid membranes
80 show lower proton conductivity, as displayed in Fig. 9(a). Mean-
while, the proton conductivity decreases with increasing GO
60 content. The incorporation of GO nanosheets with relatively poor
Weight /%

proton conducting ability diluted the density of the sulfonic acid


Nafion groups in membrane matrix, resulting in reduced proton con-
40 Nafion/DGO-0.5 ductivity. The proton conductivity of Nafion/DGO nanohybrid
Nafion/DGO-1.0 membranes is even lower than that of Nafion/GO nanohybrid
20
Nafion/DGO-1.5 membranes, as shown in Fig. 9(b). The electrostatic forces between
Nafion/DGO-2.0 –NH2/–NH– on polydopamine and –SO3H on Nafion inhibit the
dissociation of –SO3H, leading to further reduced proton
0 conductivity.
The proton conductivity of the Nafion/PGO nanohybrid mem-
0 100 200 300 400 500 600 700 800 900 branes is much higher than that of recast Nafion and increases
o with increasing PGO content, as shown in Fig. 9(c). Furthermore,
Temperature/ C
improved proton conductivity is presented obviously at elevated
temperature. The Nafion/PGO-2.0 nanohybrid membrane shows
the highest proton conductivity of 0.124 S cm  1 at 30 °C and
0.277 S cm  1 at 110 °C, which are respectively 2.1 and 2.2 times
100 that of recast Nafion membrane under the same condition. This
remarkable improvement in proton conductivity is due to the
following two reasons. Firstly, the water absorbing property of the
80 nanohybrid membranes is enhanced by the incorporation of hy-
drophilic PGO nanosheets, leading to an increased water uptake
60 that benefits the formation of continuous pathways for proton
Weight /%

transfer. Secondly, the hydrogen bond networks are formed be-


Nafion
tween the phosphonic acid groups grafted on GO nanosheets and
Nafion/PGO-0.5
40 water molecules. The networks provide additional new proton-
Nafion/PGO-1.0
conducting sites for proton hopping and as a result facilitating the
Nafion/PGO-1.5
proton transfer in nanohybrid membranes.
20 Nafion/PGO-2.0
3.6. Proton conductivity in different RH
0
The proton conductivity of Nafion, Nafion/DGO and Nafion/PGO
0 100 200 300 400 500 600 700 800 900 nanohybrid membranes was measured at 80 °C under different
o
RH. The results were presented in Fig. 10. The recast Nafion
Temperature/ C membrane displays dramatically reduced proton conductivity
with decreased RH. At 40% RH, the proton conductivity of recast
Nafion membrane is 0.0058 S cm  1, only 5.76% of that at 100% RH.
Fig. 7. The TGA curves of the pristine Nafion membrane and Nafion/GO (a), Nafion/
DGO (b), Nafion/PGO (c). The high proton conductivity of Nafion membrane in highly hu-
midified conditions is mainly attributed to its continuous hydro-
philic channels formed by interconnected ionic clusters. As the RH
decreases, the ionic clusters in Nafion become smaller and the
B. Zhang et al. / Journal of Membrane Science 518 (2016) 243–253 251

60 40
Nafion/GO Nafion/GO
50 Nafion/PGO Nafion/PGO
Nafion/DGO Nafion/DGO
30

Swelling degree / %
40
Water uptake / %

30 20

20
10
10

0 0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0
Filler Content/ % Filler content / %

Fig. 8. Water uptake (a), and swelling degree (b) of the pristine Nafion membrane and nanohybrid membranes.

0.14
Nafion
Nafion 0.14
Nafion/DGO-0.5
Nafion/GO-1
Nafion/DGO-1.0
0.12 Nafion/GO-2
-1

Nafion/DGO-1.5
-1

0.12
Proton conductivity/ S cm

Proton conductivity/ S cm

Nafion/DGO-2.0

0.10 0.10

0.08
0.08
0.06

0.06
0.04

20 40 60 80 100 120 20 40 60 80 100 120


o o
Temperature/ C Temperature/ C

0.35
Nafion
0.30 Nafion/PGO-0.5
Nafion/PGO-1.0
-1

Nafion/PGO-1.5
Proton conductivity/ S cm

0.25
Nafion/PGO-2.0

0.20

0.15

0.10

0.05

20 40 60 80 100 120
o
Temperature/ C

Fig. 9. Proton conductivity of the recast Nafion membrane and Nafion/GO (a), Nafion/DGO (b), Nafion/PGO (c) as a function of temperature.
252 B. Zhang et al. / Journal of Membrane Science 518 (2016) 243–253

phosphonic acid groups introduces efficient proton hopping


pathways which can facilitate proton transfer even without water
molecules. Consequently, the proton conducting property of Na-
-1
Proton Conductivity/ S cm

0.1 fion/PGO nanohybrid membranes at low RH is improved


significantly.

3.7. Fuel cell performance

Nafion The single fuel cell performance of Nafion, Nafion/DGO-2.0 and


Nafion/DGO-2.0 Nafion/PGO-2.0 membranes was tested at 60 °C using hydrous H2/
Nafion/PGO-0.5 O2 gases. The power density curves, as well as the polarization
0.01
Nafion/PGO-1.0 curves were shown in Fig. 11. The Nafion/PGO-2.0 membrane
Nafion/PGO-1.5 displays the best fuel cell performance with the highest power
Nafion/PGO-2.0 density of 213.12 mW cm  2 at current density of 0.59 A cm  2,
while the Nafion and Nafion/DGO-2.0 membranes show the
40 50 60 70 80 90 100 highest power density of 193.78 and 144.02 mW cm  2 at current
density of 0.53 and 0.40 A cm  2, respectively. The results, which
Relative Humidity / %
are consistent with the proton conductivity, indicate that fuel cell
Fig. 10. Proton conductivity of the recast Nafion and nanohybrid membranes as a performance is mainly influenced by proton conductivity. High
function of relative humidity.
performance of Nafion/PGO-2.0 membrane is due to the low re-
sistance and high proton conductivity of nanohybrid membrane
1.0 incorporated with phosphonic acid functionalized graphene oxide.
Nafion 250 The high content of hydrophilic PGO leads to an increased water
Nafion/DGO-2.0
uptake, and hydrogen bond networks are formed between the
0.8 Nafion/PGO-2.0
phosphonic acid groups and water molecules, generating new
Power Density/ mW cm -2

200
proton-conducting sites for proton hopping and continuous
0.6 pathways for proton transfer. Thus, the Nafion/PGO-2.0 membrane
Voltage/ V

150
exhibits the highest proton conductivity and the best single fuel
cell performance. What's more, the open circuit voltages of Nafion,
0.4
100 Nafion/DGO-2.0 and Nafion/PGO-2.0 membranes are 0.912 V,
0.918 V and 0.939 V, respectively. The Nafion/PGO-2.0 membrane
0.2 50 exhibits the highest open circuit voltage, indicating the prolonged
pathways for gas diffusion.
0.0 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Current Density/A cm-2 4. Conclusions

Fig. 11. Fuel cell performance of the recast Nafion and nanohybrid membranes. Phosphonic acid-functionalized graphene oxide (PGO) is syn-
thesized successfully and doped into Nafion to prepare nanohybrid
hydrophilic channels become narrower, resulting in an increased membranes. The PGO nanosheets disperse homogenously and
resistance for proton transfer. Moreover, at low RH, sulfonic acid show good compatibility with Nafion matrix. The Nafion/PGO
groups on Nafion cannot dissociate completely, leading to a lower nanohybrid membranes exhibit improved proton conductivity at
proton mobility [1]. Therefore, the proton conductivity of Nafion both 100% RH and low RHs compared with recast Nafion mem-
membrane at low RH can be improved by enhancing its water brane. At 100% RH, the phosphonic acid groups on GO nanosheets
retention capacity or introducing other proton acceptors such as form hydrogen bond networks with water molecules, which act as
phosphonic acid groups instead of water molecules. efficient pathways for proton hopping to enhance the proton
The Nafion/DGO-2.0 nanohybrid membrane shows lower pro- conducting capacity. The Nafion/GO-2.0 membrane shows the
ton conductivity at 100% and 80% RH, but higher proton con-
highest proton conductivity of 0.277 S cm  1 at 110 °C and 100%
ductivity at 65% and 40% RH compared with recast Nafion mem-
RH, which is about 2.2 times than that of recast Nafion. In the case
brane. At low humidity, acid-base pairs are formed by amino/
of low RH conditions, the improved water retention capacity of
imino groups on polydopamine. Sulfonic acid groups on Nafion
Nafion/PGO nanohybrid membranes restrains the shrink of ionic
can facilitate proton transfer by providing proton hopping path-
clusters, while PGO nanosheets with densely distributed phos-
ways, thus compensating for the reduction of proton conductivity
phonic acid groups introduce novel proton hopping pathways to
owing to water loss in some degree. The proton conductivity of
Nafion/PGO nanohybrid membranes is higher than that of recast facilitate proton transfer without water, resulting in improved
Nafion membrane, and increases with the PGO content. The na- proton conductivity. The highest proton conductivity of
nohybrid membrane with 2 wt% PGO content shows a proton 0.0441 S cm  1 is obtained at 80 °C and 40% RH for Nafion/PGO-2.0
conductivity of 0.0441 S cm  1 at 40% RH, which is 6.6 times higher membrane, which is about 7.6 times of that of recast Nafion.
than that of recast Nafion membrane. The strong water retention Meanwhile, the Nafion/PGO-2.0 membrane displays the best fuel
capacity of phosphonic acid groups enables these nanohybrid cell performance with the highest power density of
membranes to hold more water even at low RHs, thus restraining 213.12 mW cm  2 and open circuit voltages of 0.939 V. The che-
the shrink of ionic clusters. Moreover, since the phosphonic acid mical strategy used in this study may provide a new method for
groups can act simultaneously as proton donors and acceptors, the GO functionalization and make GO-based nanohybrid membranes
incorporation of PGO nanosheets with densely distributed as attractive proton conductors for PEM fuel cell applications.
B. Zhang et al. / Journal of Membrane Science 518 (2016) 243–253 253

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