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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
0376-7388/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.memsci.2013.08.048
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.
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.
5 m
Zeolite
layer
-alumina
substrate
Fig. 3. SEM image of the cross-section of the -alumina supported MFI zeolite
membrane.
Fig. 2. Schematic diagram of the RFB cell design and testing system.
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
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
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.)
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
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,
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.
17
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