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Abstract
This study aimed at investigating ion-exchange membrane systems using impedance spectroscopy. Nyquist plots showed that the impedance
obtained in this study described the ion-exchange membrane system well, as consisting of (i) an ion-exchange membrane immersed in solution,
(ii) electrical double layers at the membrane surface, and (iii) diffusion boundary layers arising from the interface between the ion-exchange
membrane and the electrolyte solutions. Taking into account the physical and electrochemical understanding of the ion-exchange membrane
system, an equivalent circuit was suggested to quantitatively analyze each component of the ion-exchange membrane system. To confirm the
reliability of the proposed equivalent circuit, the resistance and capacitance were estimated from the impedance data and the values were compared
with other experimental results (e.g., I –V curves). The comparison showed good agreement and validated the equivalent circuit. Moreover, the
impedance measurements made it possible to confirm the electroconvective effects in the over LCD region.
© 2006 Elsevier Inc. All rights reserved.
Keywords: Ion-exchange membrane; Electrical impedance spectroscopy; Nyquist plot; Equivalent circuit; Electroconvective effects
ing region of IEMs, etc.) in the field of IEM systems are re- Table 1
quired to be understood by new methods. Main properties of the AMX anion-exchange membrane used in this study [24]
Previous researchers have proven that electrical impedance Name Neosepta AMX
spectroscopy (EIS) is a noninvasive technique for character- Backing Poly(vinyl chloride)
izing (i) the electrical properties of materials, electrochemical Electric resistance ( cm2 ) 2.5–3.5
phenomena, and structural observations of bipolar membranes Burst strength (kg/cm2 ) 4.5–5.5
[15–19], (ii) composite membranes [20], and (iii) synthetic Exchange capacity (meq/g dry membrane) 1.4–1.7
Thickness (mm) 0.16–0.18
ion-exchange membranes [21–23]. Especially, the impedance Transport number (total cations or anions) 0.98<
studies of the bipolar membranes have provided good electro- Water content 0.25–0.30
chemical information on the bipolar junction structure and the Reinforcing Yes
intermediate region between the two ion-exchange membranes
as well as related electrochemical phenomena (i.e., the superim-
posed electric fields). Especially, Smith et al. [16] predicted the consisted of two compartments of equal volume (150 ml) sep-
approximate distance (1 nm) between the two ion-exchange arated by a membrane that was supported by rubber gaskets
membranes using the obtained impedance data. Park et al. across a circular hole of 0.785 cm2 . The details are found else-
[24,25] reported that impedance spectra well explained fouling where [27].
effects on IEM systems that were hundreds-of-micrometers do- Direct (dc) and sinusoidal alternating currents (ac) were sup-
mains. Taking account of the space resolution, the impedance plied to a pair of Ag/AgCl planar electrodes at a current scan-
measurements can be a good tool for investigating unknown ning rate of 1 µA/s for I –V curves and in the frequency range
transport phenomena in IEM systems. from 106 to 10−3 Hz for measurements of impedance spectra
In this study, we examined the analogy between current– by a potentiostat/galvanostat and a frequency response analyzer
voltage curves and impedance spectra of IEM systems in terms (AutoLab, Model PGSTAT 30, Netherlands), respectively. The
of conductive properties (i.e., resistance). Based on the im- Ag/AgCl planar electrodes minimized the water dissociation re-
pedance results, each conductive and capacitive property in the actions at the electrodes because proton/hydroxyl ions may af-
equivalent circuit as reported in [24] was quantitatively ana- fect the composition of electrolytes in the compartment for both
lyzed to describe the structures of IEM systems. Moreover, experiments. The potential difference and impedance across the
microscopic information on sublayers (i.e., electrical double membrane system were measured using two Ag/AgCl elec-
layers and microfluid flows (so-called electroconvection phe- trodes immersed into Luggin capillaries. All the experiments
nomena)) was provided at the phase boundaries between mem- were conducted at 25 ± 1 ◦ C.
brane and solution.
3. Results and discussion
2. Experimental
3.1. Impedance arising from the IEM systems
2.1. Electrolytes
The sinusoidal ac responded to the several superimposed
Potassium chloride (Sigma, St. Louis, Missouri) in reagent electric fields in IEM systems as discussed earlier. The im-
grade was used as a supporting electrolyte. KCl solutions with pedance spectra can be evaluated qualitatively and quantita-
different concentrations were used for measurement of the elec- tively. Fig. 1 shows a typical Nyquist plot of the IEM systems
trical impedance spectra and the I –V curves of the IEM sys- used in this study. The diameter of the capacitive loop decreased
tems used in this study. Deionized water (18 M cm) was used in the presence of stirring. It is believed that the decrease in
in preparing all the electrolytes. thickness of DBLs reduces impedance by ion diffusion [12,13].
This behavior can be explained by the concept of complex con-
2.2. Ion-exchange membranes
ductivity, which illustrates the characteristics of charge move-
ment and storage properties with frequency [22,28],
The Neosepta AMX (Tokuyama Soda Co., Japan) is a re-
inforced standard grade homogeneous ion-exchange membrane σ ∗ = σ + j ωε, (1)
containing quaternary ammonium groups as fixed charges for
use in general concentration or desalination [11,26]. Table 1 where σ is the conductivity and ε the dielectric permittivity of
shows their main properties as given by the manufacturer [26]. the electrical system. At a high frequency (ωε σ ), the dielec-
Prior to all the experiments, the test membranes were immersed tric permittivity term dominates in the complex conductivity.
in the desired electrolyte solution for 24 h to reach equilibrium. This means that the dielectric permittivity of the interface is
greater than that of the membrane, and current can easily pass
2.3. Measurement of current–voltage curves and electrical through the membrane without significant electrical hindrance.
impedance spectra In fact, it was observed that the impedance of the IEM sys-
tem was constant at high frequencies (not shown here), corre-
The current–voltage curves and electrical impedance spec- sponding to the conductivity of the membrane. However, at low
troscopy were obtained using an electrodialytic cell, which frequencies (ωε σ ), the conductivity term dominates in the
J.-S. Park et al. / Journal of Colloid and Interface Science 300 (2006) 655–662 657
Fig. 3. Equivalent circuit for the IEM systems used in this study, which consists
of effects of the membrane immersed in solution (SM), heterogeneous transport
(HT), and diffusion boundary layer (DBL) and is represented by a resistance
and two parallel combinations of a resistance and a constant phase element.
Zsys ∼
= (R1 + R2 ) − j ωC2 R22 ∼
= R1 + R2 . (4)
Previous researchers have used this type of the equivalent
circuit to describe a simple membrane system [16,19–21,29].
The series resistance and the parallel combination generally
correspond to the impedances arising from the solution and the
Fig. 2. Membrane effect on impedance spectra (Nyquist plots) of the AMX membrane, respectively. Thus, the membrane results in the for-
membrane in 0.01 M KCl, using the two-compartment electrolytic cell under mation of a loop. However, IEM systems should be different. It
no stirring. should be noted that the membrane is highly conductive in the
IEM systems (0.263–0.555 S/m2 according to the manufactur-
complex conductivity. This implies that the conductivity of the er’s estimate of the ion-exchange membrane conductance [26]).
DBLs is much lower than that of the ion-exchange membrane. Accordingly, the converged impedance in Eq. (3) includes the
Thus, this layer was apt to insulate the ion-exchange membrane resistance of the solution (R1 ) and membrane (R2 ) in the IEM
to some extent, resulting in high impedance to current passing system at high frequencies. It is necessary to introduce other
through the ion-exchange membrane. It makes a loop as shown electrical components into this equivalent circuit to fully de-
in Fig. 1. No capacitive loop was observed for the impedance scribe the impedance arising from the IEM system. Park et
spectrum of the IEM system in the absence of the ion-exchange al. [24] reported the equivalent circuit for IEM systems. In this
membrane, as shown in Fig. 2. It can be inferred that at low fre- study, the IEM system was analyzed using the equivalent circuit
quencies the capacitive loop depicts the electrical responses to shown in Fig. 3.
interface phenomena (e.g., DBL, heterogeneous transport [24]) The beginning part of the capacitive loop in Fig. 4 is the
originating from the ion-exchange membrane. pure resistance of the solutions and the membrane at zero phase
angle. The shift of the capacitive loops toward lower real im-
3.2. Concentration effects on the impedance spectra pedance is due to the decrease in solution resistance. It is well
known that resistance of ion-exchange membranes should be
The loop was also affected by the concentration of the elec- independent of solution concentration due to the electroneutral-
trolyte and the distance between the two reference Ag/AgCl ity between the counterions and the fixed exchangeable sites. It
658 J.-S. Park et al. / Journal of Colloid and Interface Science 300 (2006) 655–662
(a)
(b)
Fig. 6. Change of the imaginary impedance part of the IEM system with re-
spect to the reciprocal of frequency in the 0.01 M KCl solution: (a) the linear
relationship between ω−1 and −Im(Z) showing the capacitance characteristic
due to the dispersion of the membrane from 139 to 16.8 Hz and (b) the non-
linear relationship between ω−0.5 and −Im(Z) showing the fractional power
Fig. 5. Distance effect of the reference electrode on impedance spectra (Nyquist characteristic due to the dispersion of the DBL from 11 to 0.002 Hz.
plots) of the AMX membrane in 0.01 M KCl using the two-compartment elec-
trolytic cell under no stirring where the two reference electrodes are positioned
at different distances from the central membrane: 0.25, 0.50, 0.75, and 1.00 cm. phase element, CPE) circuits, expressing different relaxation
times in a complex electrochemical system. The CPE im-
is noted in Fig. 4 that a change in the diameter of loops also pedance is obtained using the following equation in the im-
occurs. The diameter decreases as the concentration of the elec- pedance representation,
trolyte increases. It is inferred that there is another impedance −Im(Z) = −Q(ω) = Y0 (j ω)−n , (5)
to restrict ionic transport from the solution to the membrane
(i.e., heterogeneous transport). Fig. 5 shows that increasing the where Y0 is the admittance (/sn ) and n the empirical parame-
distance between two reference electrodes causes a shift of the ter (0 n 1). When n = 0.5, 1, and −1, the CPE is called a
capacitive loop similar to the effect of electrolyte concentration, Warburg impedance, which is related to a diffusion process ac-
but the diameter of the loops does not change. This implies that cording to Fick’s law, a reactance by capacitance, and one by
the heterogeneous transport is related to transport phenomena inductance, respectively [21,28]. The power dependency of the
that are dependent on electrolyte concentration and occur in the constant phase element with frequency can be observed in the
heterogeneous phase (i.e., at the interfaces). plot of 1/ω vs −Im(Z), in which the slope is the reciprocal of
total admittance by Eq. (5).
3.3. Equivalent circuit of the IEM systems Figs. 6a and 6b show two different relaxations with fre-
quency. The linear relationship with ω−1 (see Fig. 6a) at fre-
Capacitive or inductive loops are often generalized as de- quencies above 16.8 Hz indicates the pure capacitance charac-
pressed semicircles by parallel R (resistance)–Q (constant teristic, according to Eq. (6). On the other hand, at frequencies
J.-S. Park et al. / Journal of Colloid and Interface Science 300 (2006) 655–662 659
Table 2
Values of electrochemical parameters obtained by fitting the experimental im-
pedance data using the suggested equivalent circuit with concentration of the
KCl solution and existence of stirring
Solution Stir- RSM RHT QHT a RDBL QDBL a
(M KCl) ring ( cm ) ( cm ) Y ∗
2 2
n ( cm ) Y ∗
2
0,HT 0,DBL n
0.01 No 134.6 42.59 1.883 1.0 17.60 0.231 0.59
Yes 135.9 26.16 0.358 0.79 – – –
(a)
be calculated by the equation
Table 3
Values of the fractional power (n) of each constant phase element obtained by fitting the experimental impedance data for the AMX membrane systems in the
absence of stirring using the suggested equivalent circuit as a function of current density
Region
Under LCD LCD Over LCD
Superimposed direct 0 6.37 19.1 30.9 33.1 34.4 35.6
current density (A/m2 )
SM n 1 1 1 1 1 1 1
HT n 1 1 1 1 0.94 0.98 1
DBL n 0.55 0.48 0.55 0.55 0.49 0.75 0.79
Note. SM, effects of the membrane immersed in solution; HT, effects of heterogeneous transport; DBL, effects of diffusion boundary layer.
4. Conclusions
Fig. 9. Dispersions of the conductance with frequency for the AMX an-
ion-exchange membrane system in 0.025 M KCl (limiting current density,
It was confirmed that the IEM systems dominantly com-
30.9 A/m2 ) as a function of current density (offset current indicated).
prised three sublayers, the ion-exchange membrane immersed
additional driving force for ion transport toward the membrane in the solution, the electrical double layers (i.e., heterogeneous
surface is created, leading to the possibility of an overlimiting transport effect), and the diffusion boundary layers, based on
current. The electroconvective effects over the LCD may dis- several impedance spectra of the IEM systems and their fitting
turb the concentration gradient in the DBL, resulting in attenu- results using the suggested equivalent circuit. Some experimen-
ating concentration polarization. This was confirmed by direct tal comparisons proved the analogy between impedance spectra
measurements of concentration gradients in the DBL using a and current–voltage curves. It is found that impedance spec-
microelectrode [27]. Hence, it is expected that the electrocon- troscopy can be an alternative way to characterize IEM systems.
vective effects may decrease the resistances arising from the Especially, impedance spectroscopy makes possible the quan-
heterogeneous transport and DBL due to the disturbance of the titative analyses of the IEM systems, which are separated into
formation of a space charge region and the relieved concentra- main components using a well-proposed equivalent circuit. Fur-
tion gradient, respectively. thermore, the separate analyses make possible investigation of
Fig. 9 shows dispersions of the conductance with frequency microscopic phenomena (e.g., electroconvection). In this re-
for the IEM systems in 0.025 M KCl. Each spectrum was mea- gard, it is considered that the impedance study can provide
sured using ac superimposed on the indicated offset dc. The useful information on the interfacial phenomena of IEM sys-
indicated dc can be categorized into three groups (i.e., un- tems.
der LCD, LCD, and over LCD; in this study, the LCD was
30.9 A/m2 ). The spectrum measured at the LCD shows the dis- Acknowledgment
tinguishable conductance change with frequency (see Fig. 9). It
This work was supported by the Core Technology Devel-
is found that LCDs for IEM systems can also be identified using
opment Program for Fuel Cells of the Ministry of Commerce,
impedance spectroscopy.
Industry and Energy, Republic of Korea.
For the IEM systems over the LCD, dispersions of the con-
ductance in the frequency range from 100 to 0.001 Hz notably
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