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Journal of Membrane Science 450 (2014) 1217

Contents lists available at ScienceDirect

Journal of Membrane Science

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

Nonionic zeolite membrane as potential ion separator

in redox-ow battery
Ruidong Yang a, Zhi Xu a, Shaowei Yang a, Ioannis Michos a, Lin-Feng Li b,
Anastasios P. Angelopoulos a, Junhang Dong a,n
a
b

Department of Chemical Engineering, University of Cincinnati, Cincinnati, OH 45221, United States

Bettergy Corp., Peekskill, NY 10566, United States

art ic l e i nf o

a b s t r a c t

Article history:
Received 9 April 2013
Received in revised form
28 August 2013
Accepted 31 August 2013
Available online 9 September 2013

The crystalline silicalite membrane has been demonstrated as an effective ion separator for acidic
solutions of vanadyl sulfate and for potential application as a proton-permselective electrolyte
membrane in the all-vanadium redox-ow battery. Silicalite contains uniform channels with an effective
diameter of 0.56 nm, which permits the small H3O ions to diffuse through but is impermeable to the
large hydrated multivalent vanadium ions due to steric effects. Unlike conventional polymeric ion
exchange materials, silicalite is nonionic and its proton conductivity relies on the electric eld-driven
H3O transport through the sub-nanometer pores. The silicalite membrane exhibits high proton
selectivity relative to vanadium ions and a signicantly reduced self-discharge rate compared to that
of Naon ion exchange membranes.
& 2013 Elsevier B.V. All rights reserved.

Keywords:
Zeolite membrane
Ion separation
Redox-ow battery

1. Introduction
Redox-ow batteries (RFBs) are promising for electrical energy
storage in distributed renewable power systems and large-scale
energy grids because of a number of advantages relative to solid
state storage devices. Advantages include simple electrode reactions,
separated cell stack and storage tanks, modularity, rapid recharge by
direct solution replacement, small environmental footprint, and low
cost [1,2]. The RFB operates by electrode reactions of dissolved ions
constituting red-ox couples:
negative electrode :
positive electrode :

ma

Mm
A ae 2MA

M nC b be 2M nC

1
2

where MAm/MAm a and MCn/MCn b are reduced/oxidized states of

metal ions in the negative (anode) and positive (cathode) compartments, respectively. MA and MC metal ions can be elementally
identical or different [2]. As schematically shown in Fig. 1, during
battery operations, the electrons go through the external circuit,
while the nonreactive ionic charge carriers, often protons, transfer
internally through the ion exchange membrane (IEM). The IEM not
only plays a key role in determining the battery energy efciency and
lifetime but also contributes substantially to the RFB cost [3].
n

Corresponding author. Tel.: 1 513 556 3992.

E-mail address: dongj@ucmail.uc.edu (J. Dong).

0376-7388/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.memsci.2013.08.048

Peruorosulfonic acid polymers, such as Naons which is

commonly considered as benchmark, were the rst choice IEM
candidates for RFB development because of their high proton
conductivity and the good stability they had already demonstrated
in proton-exchange membrane fuel cells. However, when used in
the extremely acidic and oxidizing RFB aqueous electrolyte solutions, the polymeric IEMs experience metal ion crossover and
polymer degradation that limit the cell efciency and lifetime [1,4].
These deciencies are inherent to the structural and chemical
properties of the peruorosulfonic acid polymers. Hydrated IEMs
such as Naons lms contain hydrophilic sulfonic acid groups
that form nanometer-size water channels and pockets by selforganization within an otherwise hydrophobic matrix. These
water channels are typically 24 nm in diameter and provide
conduits for the fast transport of protons under the gradients of
electrical or chemical potentials [5]. The exible structure of the
water-swollen polymer, however, also permits transport of the
larger-size hydrated metal ions [4].
Reduction of metal ion crossover has been reported when
inorganic or organic nanoparticles (e.g., SiO2) are incorporated
into the polymer matrix to reduce the width of the water channels
[6] as well as when as low-conductivity modiers are incorporated
to increase the transfer resistance for multivalent cations [7].
Attempts have also been made to reduce pore size of polymeric
membranes by deposition of silica on the internal pore wall of
nanoltration membranes to improve the proton selectivity by
increasing steric resistance to large cations [8,9]. There have also
been efforts to develop partially uorinated and nonuorinated

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R. Yang et al. / Journal of Membrane Science 450 (2014) 1217

Anode

IEM

Cathode

MAm

MAm+b

MCn+a

MCn

Charge

e-

MCn+a

MAm

MCn

e-

H+
e-

e-

Anode

IEM

MAm+b

e-

H+

e-

Cathode

13

Discharge

e-

e-

Fig. 1. Schematic showing the electron and proton transfer in an RFB during charging (left) and discharging (right) processes.

polymer IEMs for ion selectivity enhancement and cost reduction

[10]. Despite substantial progress made in recent years, the
improvement of ion selectivity by reducing the size of water
channels is ultimately limited by the swelling and exible nature
of the peruorosulfonic acid polymers. Furthermore, polymer
degradation in strong oxidizing solutions remains a concern,
especially for partial- or nonuorinated IEMs [11].
Here we demonstrate the nonionic molecular sieve zeolite lm
for effective proton/metal ion separation and its potential application as an alternative electrolyte membrane in an all-vanadium
RFB (VRFB). Zeolites are crystalline aluminosilicates with large
porosity and uniform pore sizes of molecular scale dened by
specic crystallographic structures. Membranes of small pore
siliceous zeolites such as MFI-type, which have no ion exchange
capacity, have been theoretically and experimentally shown to
separate water from dissolved alkaline metal ions by sizeexclusion (steric) effects [12,13]. The zeolite membranes allow
transport of water molecules but reject metal ions, which are
strongly hydrated in aqueous solutions, making them too large to
enter the zeolitic channels. Because the number of water molecules tied to a metal ion increases with the ion charge density, the
hydrated multivalent metal ions involved in RFB systems are
typically very large ( 40.6 nm [14]). However, proton exists in
water in the form of H3O hydronium, which is a polyatomic ion
with charge density too small to form hydration shells and thus
has a much smaller size. In this study, the siliceous MFI-type
zeolite (i.e., silicalite) membrane supported on macroporous alumina disc has been investigated for ion separation and as an
IEM in the VRFB system. The silicalite is known to be intrinsically
inert in oxidizing environments and chemically stable in strongly
basic and acidic solutions. The material contains nearly cylindrical
channels with an effective diameter of 0.56 nm, which is expected
to be permeable for H3O but inaccessible to the large hydrated
multivalent metal ions.

2. Experimental
2.1. Membrane preparation and characterization
The silicalite membrane was supported on a 25-mm diameter
porous -alumina disc that had a thickness of 2 mm, porosity of
2730%, and an average pore size of dp 0.07 m. For the
in-situ synthesized silicalite membrane, the effective area (Aeff) is
given by Am , where Am(2.54 cm2) is the straight forward area
of the membrane excluding the area covered by the O-ring seals.

The zeolite membrane was synthesized by in-situ crystallization

from an aluminum-free precursor solution with a molar composition of 0.33(SiO2):0.1(TPAOH):0.017(NaOH):5.56(H2O). The tetrapropylammonium hydroxide (TPAOH) is the structure directing
agent (SDA). The synthesis procedure is similar to that reported in
our previous publication [15]. The hydrothermal crystallization
was conducted in an autoclave at 180 1C and autogenous pressure
for 17 h. The hydrothermal synthesis process was repeated once to
minimize the intercrystalline pores after the rst lm growth. The
membrane recovered from the synthesis solution was thoroughly
washed by DI water, dried at 100 1C overnight, and then red at
500 1C for 6 h to activate the zeolitic pores by burning off the SDA
molecules. Although a very small amount of Al3 ions from the
substrate could incorporate into the zeolite framework near the
zeolite/substrate interface, the membrane was previously veried
to be aluminum-free near the outer surface [16]. The silicalite
membrane was tested by helium permeation and proton diffusion
before template removal to verify the absence of pinholes. After
calcination, the membrane was further tested by permeation of
pure helium and a 50(v)/50(v) CO2/H2 gas mixture, respectively, at
room temperature and atmospheric pressure to check the quality
of the membrane.

2.2. Ion permeation

The proton/vanadyl ion (VO2 ) transport selectivity values of
the silicalite membrane, the bare alumina substrate, and commercial Naons 117 membrane were evaluated by the conventional
diffusion experiment [9] performed in the RFB cell described in the
next section. During the measurement, 20 ml of 4/7 M VO2
(VOSO4  46H2O, 99.9%, Aldrich) sulfate solution in 4/7 M H2SO4
was circulated on one side of the membrane and 20 ml of 1 M
MgSO4 solution was circulated on the other side. The 1 M MgSO4
solution was used in the permeate side to minimize the osmotic
pressure difference and maintain equivalent ionic strengths
between the two sides. The pH value and VO2 concentration in
the Mg2SO4 solution were continuously monitored using a pH
meter (Thermo Scientic Orion 320) and a UV/vis spectrometer
(with actual VO2 detection limit of  0.0001 M), respectively.
The H /VO2 ion selectivity (H /V4 ) of the zeolite membrane
was then estimated based on their respective measured uxes.
A diffusion study was also performed on an identical zeolite
membrane with the permeate side lled with DI water instead
of the 1 M MgSO4 solution to observe the H /V4 and H ux
under osmotic pressure.

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R. Yang et al. / Journal of Membrane Science 450 (2014) 1217

5 m

Zeolite
layer
-alumina
substrate
Fig. 3. SEM image of the cross-section of the -alumina supported MFI zeolite
membrane.

3. Results and discussion

Fig. 2. Schematic diagram of the RFB cell design and testing system.

2.3. RFB performance

The single cell VRFB was constructed by mounting the silicalite
disc membrane between two carbon felt electrode plates with an
electrode-to-membrane spacing of 5 mm on both sides (Fig. 2).
The cell was operated using the circulated two-chamber conguration and a Gamry Reference-600 unit connected to a computer workstation. This electrode-membrane assembly scheme
was used in the present study because the same setup can be
conveniently used to assess membrane diffusion under conditions
similar to those present during cell operation.
In charged state, the negative and positive electrolyte solutions
were10 ml of 2 M V2 sulfate in  3 M H2SO4 and 10 ml of 2 M
V5 (VO2 ) sulfate solution in 1 M H2SO4, respectively. These
electrolyte solutions were obtained by charging starting solutions
containing 2 M VOSO4  46H2O (99.9%, Aldrich) and 2 M H2SO4.
Silicalite membrane VRFB performance was evaluated by measuring the OCV decay curve, the chargedischarge curves, and the
polarization curve at room temperature. The measurements for
the polarization curves were completed typically within a short
time span of 30 min to ensure that not more than a 2% decrease in
OCV was caused by discharge during the experiments. The total
internal resistance of the Z-VRFB was estimated using the linear
section of the polarization curve where changes in electrode
activation and mass transport over-potentials are insignicant.

2.4. Electrical resistance

The internal Ohmic resistances of the VRFBs equipped with the
supported silicalite membrane, the bare porous -alumina substrate, and Naon 117 lm were also measured during battery
operation by electrochemical impedance spectroscopy (EIS) using
the Gamry Reference-600. The electrical resistance of the
silicalite membrane was measured when both the positive and
negative chambers lled and circulated with DI water, acid-free
0.5 M VO2 solution, and 0.5 M VO2 solution with 0.5 M H2SO4,
respectively, to verify that the ionic conductivity of the zeolite
membrane relies primarily on protons and not the metal ions.

3.1. Zeolite membrane

The polycrystalline silicalite membrane synthesized was of
random crystal orientation with a thickness of 58 m according
to its cross-section SEM image shown in Fig. 3. The membrane had
an He permeance of 1011 mol/m2 s Pa before SDA removal,
indicating that the as-synthesized membrane was free of pinholes.
The proton diffusion test before ring also showed no appreciable
H transport through the membrane in 48 h, which further
demonstrated that no large defects existed in the membrane layer
and the membrane was sealed well in the liquid environment.
After template removal, the membrane exhibited a room temperature He permeance of 2.3  10  7 mol/m2 s Pa and a CO2/H2
(equimolar feed) separation factor of  0.4 that veried the
complete activation of zeolitic pores without crack formation
during the calcination process. These results demonstrate that
the silicalite membrane was of reasonably high quality.
3.2. Proton/VO2 transport selectivity
Ion diffusion experiments were performed by circulating 20 ml
solution of 0.57 M VO2 in 0.57 M H2SO4 on one side of the
diffusion cell and 20 ml of 1 M MgSO4 solution on the other to
balance the osmotic pressures and ionic strengths. The experimental data of the diffusion tests for the silicalite membrane, bare
alumina substrate, and the Naons 117 lm are presented in
Fig. 4. Vanadium ion was undetectable in the permeate side MgSO4
solution after 72 h of continuous circulation whereas a proton
(H3O ) ux of 2.13 mol/cm2 h was recorded in the same period.
The characteristic light absorption peak for VO2 appeared in the
MgSO4 solution after 74 h but the intensity was at the UV/vis
instrument detection limit (0.0001 M VO2 ). The ux of VO2 was
therefore less than 0.038 mol/cm2 h and the H /VO2 selectivity
was greater than 56 by conservative estimation. The minimal
VO2 crossover likely occurred through the small amount of
nanometer-sized inter-crystal pores in the polycrystalline silicalite
membrane [17]. The bare substrate showed a H /VO2 selectivity
of only 1.5 due to the large pore size (0.070.1 m) whereas the
Naon 117 exhibited an H /VO2 selectivity of 19. The substrate,
because of its small porosity (0.270.3) and very large thickness,
had an H ux (16.8 mol/cm2 h) lower than the Naon membrane (67.0 mol/cm2 h). The diffusion test with DI water on the
permeate side also showed negligible VO2 in the DI water after
12.3 h of operation and recorded a proton ux of 2.36 mol/cm2 h,

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R. Yang et al. / Journal of Membrane Science 450 (2014) 1217

which is close to the value of 2.13 mol/cm2 h obtained when the

balancing MgSO4 solution was used. These observations are consistent with a size exclusion mechanism.

2.E-2

silicalite mem - H+
silicalite mem - V4+
substrate - H+
substrate - V4+
Nafion 117 - H+
Nafion 117 - V4+

Concentration, M

2.E-2

1.E-2

5.E-3

0.E+0
0

4
Time, h

Fig. 4. Proton and V4 (VO2 ) ion concentration in the permeate side MgSO4
solution as a function of time.

1.8

1.6

Supported zeolite membrane

OCV (V)

1.4
Nafion-117
1.2

1.0
Alumina substrate alone
0.8

0.6
0

100

200

300

400

Time (h)
Fig. 5. The OCV decay curve of the Z-VRFB in comparison with those using alumina
substrate and Naon 117s as IEMs.

15

3.3. OCV decay

The VRFB performance tests used 10 ml of 2.0 M V3 /V2
sulfate in 3 M H2SO4 and 10 ml of V4 /V5 sulfate solution in
1 M H2SO4 as the negative and positive electrolyte solutions,
respectively. Fig. 5 shows the OCV decay curve for the zeolite
membrane-equipped VRFB (Z-VRFB) in comparison with those of
the VRFBs using the bare -alumina substrate and Naon 117s
lm (180-m thick) as IEMs and measured under identical conditions. The OCV of the Z-VRFB was much higher than the VRFBs
equipped with the bare substrate and Naon 117 membrane. Also,
the electrolyte solutions fully charged in the Z-VRFB displayed
characteristic colors of pure V2 (laneder) and V5 (yellow)
solutions, indicating a near 100% state of charge (SOC) achieved
in Z-VRFB (Fig. 6). In contrast, the electrolyte solutions charged in
the VRFB with Naon IEM (Naon-VRFB) did not exhibit the same
level of color purity. Color mixing with the Naon IEM likely
occurs due to a combination of ion crossover and lower SOC. The
OCV of the Z-VRFB remained high and decreased only slightly
(from 1.66 V to 1.50 V) over a time period of 384 h while the bare
substrate caused the OCV to drop rapidly from 1.27 to 0.88 V in
just 12 h. The OCV decay rate of the Z-VRFB was also signicantly
slower than that of the Naon-VRFB in that the OCV of the former
only started to drop sharply after about 280 h. These observations
indicate that the silicalite membrane has superior ion separation
ability relative to the Naon 117 IEM.

3.4. Chargedischarge curves

The chargedischarge curves were measured for the Z-VRFB
using the same charging (ich) and discharging (idisch) current density
of 37.5 mA/cm2 (on the basis of active silicalite membrane area).
Fig. 7 presents the result of two cycles of chargedischarge operation excluding the initial charging process for electrolyte solution
preparation. The cut-off voltages for charging and discharging
processes were 2.4 V and 0.6 V, respectively. The results demonstrate that the silicalite membrane is functional as an electrolyte
membrane for proton transport in the VRFB. Based on the second
cycle in Fig. 7, the Z-VRFB achieved a chargedischarge efciency
(C idisch t disch =ich t ch ) of 94% and average charging (V Ch ) and
discharging voltages V Disch of 1.89 V and  1.0 V, respectively,
which give an energy efciency (E C V disch =V ch ) of  50%.
The relatively low E of the Z-VRFB investigated here resulted
mainly from the large thicknesses of the silicalite membrane
(58 m) and the substrate (2000 m) as well as the large gaps
(5 mm) between the membrane and electrodes, all of which are
expected to cause high Ohmic resistances. The high internal
resistance of the Z-VRFB cell is evidenced by the large slope of
the polarization curve (Fig. 8) [18], which gives an estimated

Fig. 6. Photographs showing colors of electrolyte solutions in the positive (V5 ) and negative (V2 ) sides after being fully charged: (left) Z-VRFB; (right) Naon-VRFB. (For
interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

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R. Yang et al. / Journal of Membrane Science 450 (2014) 1217

2.5

Voltage (V)

2.0

1.5

Charge

Charge

1.0
Discharge

Discharge
0.5
0

20

40

60

Time (h)
Fig. 7. Chargedischarge curves for the Z-VRFB (current density 37.5 mA/cm2).

ux than that of the Naon lm (Fig. 4). The ASR of the Z-VRFB was
 10.8 cm2 after porosity correction and is close to the value
found from the polarization curve. Since the Naon 117 membrane
is known to have an ASR of o1 cm2, the resistance of the
solution lled gaps and other components (e.g., interfaces) in the
cell was estimated to have a comparatively large value of  3.7
for the cell conguration with electrolyte gaps between membrane
and electrodes. The EIS measurement for the no-gap sandwich
assembly of the silicalite membrane exhibited a substantially
reduced total cell resistance of 9.1 as shown in Fig. 9.
To further verify that ion conductivity in the silicalite membrane relies on proton transport through the zeolitic pores, EIS
measurements were also performed in the cell setup for the
silicalite membrane when both sides of the membrane were in
DI water, acid-free 0.5 M VO2 solution, and the 0.5 M VO2
solution with 0.5 M H2SO4. The resistance was too large to be
measured by EIS in either DI water (4 150 k) or the acid-free
0.5 M VO2 solution (4 25 k). The ASR of an IEM is determined

12

1.6
1.4

Silicalite mem
Substrate
Nafion 117
Silicalite no-gap

8
4
imag

1.0
0.8

-Z

Voltage (V)

1.2

0.6
0.4

-4

With gap
0.2
0.0

No-gap
0

20

-8
40

60

80

100

Current density (mA/cm2)

resistance of 12 cm2. To evaluate the effect of the electrolyte

gaps on the internal resistance, the carbon felt electrodes were put
in direct and tight contact with the zeolite membrane by Teon
plates containing channels for the electrolyte solutions to ow
over the outer surfaces of the electrodes. As in the original
conguration, this sandwich assembly had the porous alumina
support facing the carbon felt electrode. In this case, a much more
shallow polarization curve was obtained (also shown in Fig. 8)
with an estimated cell resistance of  6 cm2 for a new silicalite
membrane made under identical conditions.
3.5. Electrical resistance
EIS measurements were performed in electrolyte solutions to
further estimate the cell resistances for a fresh silicalite membrane, the bare substrate, and the Naon 117 lm. Results are
presented in Fig. 9. The internal resistances of the VRFBs equipped
with the supported silicalite membrane, the bare porous alumina
substrate, and the Naon 117 membrane were 14.2 , 5.7 , and
4.1 , respectively. The resistance of the silicalite layer alone is
therefore estimated to be around 8.5 according to the difference
between the supported silicalite membrane and bare substrate.
The cell resistance with the substrate alone was 1.6 greater than
that of the Naon 117. This difference is due to the small porosity
and large thickness of the substrate, which yielded a lower proton

15

20

Fig. 9. Results of EIS measurements under RFB operation conditions for the
supported silicalite membrane, the bare alumina substrate, and the Naon 117
membrane in cell structure with gaps and for the silicalite membrane in a no-gap
assembly.

800
700
600

-Zimag,

Fig. 8. Polarization curves of the Z-VRFB.

10
Z real,

500

DI Water

400

Non-acdic V4+
Acidic V4+

300

20

200

10

100

-10
0

-100
0

1000

2000
Zreal,

50 100 150

3000

4000

Fig. 10. Results of EIS measurements for the silicalite membrane in different
solutions including DI water, acid-free 0.5 M VO2 (VOSO4) solution, and 0.5 M
VO2 (VOSO4) solution with 0.5 M H2SO4.

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R. Yang et al. / Journal of Membrane Science 450 (2014) 1217

by the ion permeability P b;i ( C i Di , where Ci and Di are ion

concentration and transport diffusivity inside the membrane)
and the membrane thickness (), using ASR RT=zi 2 F 2 C i Di where
Zi and F are the charge of the ion and Faraday constant, respectively. Because metal ions are too large to enter the zeolitic pores
and the proton concentrations in the electrolytes are very low, the
Ohmic resistance of the nonionic silicalite membrane is extremely
high in DI water and acid-free VO2 solution (pH  6.8). When
0.5 M H2SO4 was added to the 0.5 M VO2 solution, the resistance
decreased sharply to 26.3 , indicating that proton but not metal
ion transport is the cause of electrical conductivity in the nonionic
silicalite lm (Fig. 10).
4. Conclusion
The nonionic silicalite membrane is permeable to protons
(H3O ) in aqueous solutions and highly effective in preventing
vanadium ion crossover because the hydrated multivalent metal
ions are too large to enter its 0.56 nm-diameter channels. The
present study has demonstrated that silicalite lms are attractive
alternatives to polymeric membranes as ion separators for VRFBs.
The silicalite membrane-equipped VRFB (Z-VRFB) has achieved high
Columbic efciency and low self-discharge rate compared to those
of Naon 117, which is a widely used benchmark of polymeric IEM.
Although the current Z-VRFB exhibited limited voltage efciency
due to large Ohmic resistance of the supported zeolite membrane,
future performance enhancement is anticipated through optimization of the membrane structural and chemical properties. For
example, the ASR of the silicalite membranes may be signicantly
lowered by minimizing the membrane thickness. Furthermore, the
hydrophilic Al-containing MFI zeolite(ZSM-5) membranes were
found to have water permeability more than a hundred times
greater than the hydrophobic silicalite membranes without compromising the metal ion rejection rate [19]. Consequently, making
the MFI membranes more hydrophilic may also dramatically
enhance the proton permeability. One may also synthesize the
zeolite membrane on a porous carbon substrate, which simultaneously serves as an electrode material and eliminates the resistance associated with the aluminum support. Such a conguration
would also substantially reduce the weight of the battery.
Acknowledgment
This work was supported by the U.S. National Science Foundation (CBET-1263860, CBET-0854203 and IIP-1142695).

17

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