Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 473479

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Journal of the Taiwan Institute of Chemical Engineers

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Preparation of activated carbon sheet electrode assisted electrosorption process

Chia-Hung Hou a,*, Jing-Fang Huang b, Hong-Ren Lin a, Bo-Yan Wang a
a
Department of Environmental Science and Engineering, Tunghai University, Taichung 40704, Taiwan
b
Department of Chemistry, National Chung Hsing University, Taichung 40227, Taiwan

A R T I C L E I N F O A B S T R A C T

Article history: Electrosorption, dened as potential-induced sorption on the surface of charged electrode, is a promising
Received 17 September 2011 method for water purication and desalination. To prepare carbon electrodes assisted electrosorption
Received in revised form 22 November 2011 process at the point of economical view, activated carbon powder was coated with polyvinylidene
Accepted 8 December 2011
uoride (PVDF) binder in a thin sheet-like formulation. Electrochemical properties of the fabricated
Available online 18 January 2012
carbon electrodes were analyzed via cyclic voltammetry and galvanostatic charge/discharge experi-
ments. From the results, the electrosorption characteristics of the fabricated electrodes can be improved
Keywords:
in KOH solution. Increasing the PVDF content diminishes the specic capacitance and increases electrical
Electrosorption
resistance in electrosorption. The carbon electrode prepared with 10 wt% PVDF has enough mechanical
Capacitive deionization
Activated carbon strength, good electrochemical stability, and favorable capacitive characteristics for electrosorption of
Voltammetric capacitance ions. From the electrosorption experiments of capacitive deionization, the electrosorption efciency and
Electrical double layer electrosorption capacity for 0.002 M NaCl solution with an applied potential of 1.2 V are 96.7% and
44.5 mmol/g, respectively. The regeneration of the polymer-binder carbon electrode can be achieved by
depolarizing the electrode at 0.0 V. It indicates that electrosorptiondesorption of ions is a reversible
process, with respect to electrical double layer formation on the charged surfaces of carbon electrode.
Therefore, the PVDF-bonded activated carbon sheet electrode would be a desirable electrode for
capacitive deionization.
2011 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction electrodes for supercapacitors or electrical double layer capacitors

Nanoporous carbon materials, such as activated carbon, carbon
ber, and carbon nanotube, are ubiquitous and indispensable in a
wide range of environmental applications due to their micropo-
rosity, high surface area, and high adsorption capacity [1]. More
specically, as molecular sieves for gas purication and separation,
activated carbons with selecting pore size distribution can
separate target molecules (gases, organic vapors, etc.) by their
difference in diffusion rate and adsorption capacity [2]. Activated
carbons can be further recognized as high-capacity adsorbents and
thereby, they are widely used to remove environmental con-
taminants such as organic compounds and heavy metals in liquid
phase [1,3,4].
During the last years, another important aspect of carbon
materials is their relatively good electrical conductivity. The
surface charge of carbon materials can be easily regulated by
applying electric potential or current to store ions. Therefore,
taking advantages of the combination of high specic surface area,
good electrical conductivity, and high electrochemical stability,
makes carbon materials suitable for use in energy storage as
* Corresponding author. Tel.: +886 4 23590121; fax: +886 4 23504276.
E-mail addresses: chhou@thu.edu.tw, chhou0320@gmail.com (C.-H. Hou).
[5]. In this application, by consisting of a pair of polarizable carbon
electrodes, large quantities of energy can be stored or released via
manipulation of electrical double layer formation at the electrode/
electrolyte interface. In other words, the capacitor performance,
referred to the amount of electric charge separation, can be
determined by the surface area available for ions electrosorbed
onto the charged surface. A porous carbon material with a higher
specic surface area may contribute to more electrical energy
storage.
Currently, due to the shortage of water and energy resource,
capacitive deionization (CDI), or referred to electrosorption, has
been developed as a promising nanotechnology to solve the critical
problem [68]. Basically, the CDI method is an electrosorption
(dened as potential-induced sorption on the surface) process,
following the same principle of charge separation in electrical
double layer capacitor. By applying a potential difference between
a pair of nanoporous electrodes, the positively charged electrode
attracts anions and the negatively charged electrode electro-
adsorbs cations. At this point, the ions are electrostatically
separated from the bulk solution and then held in the double
layer region within charged nanoporous carbon materials.
Therefore, the puried water is delivered as the product.
Furthermore, by canceling the potential difference, the ions are
quickly released back to the bulk solution. Compared to other

1876-1070/$ see front matter 2011 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jtice.2011.12.003
474 C.-H. Hou et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 473479

desalination processes like reverse osmosis and electrodialysis, CDI discharge curves. In addition, the carbon electrodes were
is expected to be a more energy efcient, environmentally friendly pretreated in KOH solution to improve the electrosorption
process for water purication and desalination [6,8]. characteristics. Electrosorption experiments were carried out with
A number of studies reported that CDI process using carbon a CDI unit cell to assess the electrosorption performance and to
materials as nanoporous electrodes has succeeded to remove a provide a fundamental understanding of CDI process.
variety of unwanted ions or charged contaminants from aqueous
solutions as means of desalinating brackish water, softening
hardness, or remediating ground water [913]. Nanoporous carbon 2. Materials and methods
materials, such as carbon aerogel, activated carbon, carbon ber,
and carbon nanotubes, constitute very attractive materials because 2.1. Preparation of carbon sheet electrode
of their high surface area and their good electric conductivity [14].
Also, mesoporous carbons have been developed as CDI electrodes In this work, activated carbon powder (Filtrasorb 400,
with good electrochemical properties and reversibility [1315]. Chemviron Carbon Inc., USA, specic surface area = 1124 m2/g)
More recently, graphene that is a single layer of graphite with and polyvinylidene uoride (PVDF, M.W. = 534,000, Sigma
atomistic thickness has received attention as a potential material Aldrich) polymer binder were used to manufacture nanoporous
for CDI [16]. However, the manufacturing cost of nanoporous carbon sheet electrodes. Various weight ratios of activated carbon
carbon electrodes is one of the most important considerations for powder and PVDF polymer were used to determine the optimum
promoting CDI process at the current stage. From commercial composition of carbon electrode. N,N-Dimethylaceurodie (DMAc,
aspect, it is essential to fabricate nanoporous carbon electrodes 99%, Alfa Aesar) was used as a solvent. Fig. 1 shows the overall
with strong mechanical stability, low manufacturing cost, and high experimental procedure for the fabrication of a carbon sheet
sorption capacity. As well known, activated carbon powder has electrode by mixing activated carbon powder and PVDF binder. The
inexpensive price and high specic surface area (10002000 m2/g). mixture was stirred for 6 h to ensure homogeneity. Then, the
But, the limitation of conventional activated carbon electrodes (i.e., carbon slurry was dried in a 120 8C oven for 2 h to form the carbon
packed beds) is characterized by a low conductivity, irregular pore sheet electrode. Each electrode had the effective surface area of
structures, and high electrical or mass-transfer resistance, assis- 80 mm  80 mm, thickness of 0.38 mm, and weight of about 1.5 g.
tant with lower deionization efciency [17]. In addition, the The carbon sheet was further dried in 80 8C vacuum oven for 2 h to
manufacturing method that uses a roll press and a polymer binder, ensure that all organic solvents present in the micropores were
which is used to hold the activated carbon powders together in a removed from the electrode. Furthermore, the PVDF-bonded
sheet-like formulation, may result in chemical attack, poor carbon sheet electrodes were treated with 1 M KOH solution at
electrical conductivity, and reducing electrosorption capacity of room temperature for 24 h. After immersing in KOH solution, the
electrodes. On the other hand, the benet using polymer binders is carbon electrode was washed by D. I. water, and dried completely
that a thin sheet electrode is very convenient and desirable in at 70 8C under vacuum for 6 h.
electrosorption process.
Recently, several researchers have found that nanoporous
carbon electrodes, fabricated by mixing activated carbon powder
in a polymer solution on the current collector, can be treated as
desirable candidates for electrosorption of ions [1820]. For
example, a carbon sheet electrode was prepared by mixing carbon
powder, polytetrauoroethylene (PTFE) binder, and conductive
carbon black [20]. Choi [18] also fabricated a carbon electrode with
activated carbon powder using polyvinylidene uoride (PVDF) as a
polymer binder through a drying process. It is noted that the
deionization efciency of carbon electrodes depends on surface
properties (i.e., surface functional groups and surface polarity) of
the material itself. With that regard, the use of hydrophobic
polymer-binder such as PVDF could diminish the pore accessibility
of carbon electrode, corresponding to poor electrochemical
properties. Additionally, the deionization efciency of activated
carbon electrodes can be improved by surface modication via
chemicals (i.e., KOH or HNO3 solution) and metal oxide nano-
particles (i.e., TiO2) to increase the functional groups and surface
density of hydrophilic group, respectively [2123].
Nanoporous carbon electrode is a crucial factor affecting the
electrosorption performance and electrosorption capacity of the
material itself. More specially, carbon electrode with a thin sheet-
like formulation is very useful and convenient for the utilization in
CDI process. With respect to this point, the use of polymer binder is
necessary to x activated carbon powders in electrosorption;
whereas it may cause poor electrochemical properties. The object
of this study is to fabricate a nanoporous carbon sheet electrode,
made from activated carbon powder and polymer binder in a
simple process, to have strong mechanical stability, good
electrochemical properties, and high electrosorption capacity for
CDI. The capacitive behavior of carbon electrodes with various
polymer binder contents was examined by voltammetric experi- Fig. 1. Overall experimental owchart for the fabrication of a carbon sheet electrode
ments, including cyclic voltammetry and galvanostatic charge/ made from activated carbon powder and PVDF polymeric binder.
 C.-H. Hou et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 473479 475

2.2. Characterization conditions were repeated to conrm the reproducibility of the

A surface and pore size analyzer (TriStar II 3020, Micromeritics
Inc., USA) was employed to obtain the nitrogen adsorption
desorption isotherm and specic surface area via the Brunauer
EmmettTeller (BET) method from the nitrogen adsorption data in
the relative pressure range of P/P0 = 0.99. The carbon electrodes
were further characterized by scanning electron microscope (SEM)
image using a JEOL, Inc., JSM-7401F electron microscope.
2.3. Electrochemical measurement
The electrochemical properties on capacitive deionization for
activated carbon electrodes were tested by cyclic voltammetry and
galvanostatic charge/discharge experiments. The voltammetric
measurements were carried out on an electrochemical worksta-
tion (CHI 627D, CH Instruments, Inc., USA) with a three-electrode
cell. The working electrode was a platinum wire attached to a small
piece of carbon material (23 mg), the counter electrode was a
large carbon material with another platinum wire, and the
reference electrode was the BAS model RE-1 (Ag/AgCl electrode
in a 3 M NaCl electrolyte solution). Cyclic voltammograms for
assessing the voltammetric capacitance of carbon electrode were
obtained in a potential window of 0.6 to 0.4 V with a scan rate of
10 mV/s. To test the charge/discharge performance, the electro-
chemical cell was charged with constant current (0.1 A/g) up to a
voltage of 0.8 V, and discharged with constant current (0.1 A/g)
down to a voltage of 0.0 V. The electrolyte solution was 1 M sodium
chloride (NaCl) (Merck).
The specic capacitance was calculated from the CV curves by
the following equation:
i respectively. More specically, the isotherms of PVDF10 and
C (1)
vm
where C represents the specic capacitance (F/g). i and v are the
current density (A) and scan rate (V/s), respectively. m is the mass
of activated carbon electrode (g). In the cyclic voltammetry
experiments, the measured electrical current is divided by the scan
rate to give the capacitance. Then, the capacitance can be divided
by the sample weight of carbon electrodes to yield the specic
capacitance.
2.4. Electrosorption experiments of capacitive deionization
Electrosorption experiments were performed in a continuously
recycling system to test the CDI performance of the fabricated
carbon electrodes. The system was composed of an electrosorption
unit cell, a peristaltic pump (MP-1000, EYELA, Japan), a conductiv-
results.
In the experiments, the electrosorption efciency (%) is dened
as follows:
C0  Ce
Electropsorption efficiency (2)
C0
where C0 and Ce are the initial and equilibrium concentrations (M),
respectively.
The electrosorption capacity (mmol/g) can be dened as
follows:
C 0  C e  V
Electrosorption capacity (3)
m
where V is the volume of solution (L).
3. Results and discussion
3.1. Porous characterization
Fig. 2 shows the nitrogen adsorptiondesorption isotherms for
activated carbon sheet electrodes prepared by different weight
ratios of polyvinylidene uoride PVDF. PVDF10, PVDF20, PVDF30,
and PVDF40 represent the activated carbon sheet electrodes mixed
with 10, 20, 30, and 40 wt% PVDF polymer binder. As observed, all
activated carbon sheet electrodes exhibit a typical IUPAC isotherm
of type IV with a hysteresis loop, usually associated with a mixture
of mesoporous and microporous characters. The plateau of the
isotherm at high relative pressures (P/P0) results from of the
presence of mesoporous structure. For the PVDF10 electrode, the
percentages of the surface area attributed to mesopores and
micropores to the total surface area are 54.6 and 45.4%,
PVDF20 display a relatively large hysteresis loop, suggesting the
existence of larger size pores and higher specic surface area. As a
result, the BET specic surface area for the PVDF10, PVDF20,
PVDF30, and PVDF40 electrodes can be determined as 984, 680,
399, and 269 m2/g, respectively. Increasing the content of PVDF
binder in carbon electrode decreases the specic surface area.
In addition, Fig. 3(a) and (b) shows the SEM images of the top
view and cross-section view of PVDF10 electrode, which consists of
90% carbon and 10% PVDF. As can be seen, activated carbon
powders are bound together by PVDF binder to form a uniform
electrode layer. Because PVDF has good chemical stability, the
manufactured carbon electrode possesses enough mechanical
strength in electrosorption process. On the other hand, as shown in
1200
Quantity Adsorped (cm /g STP)

ity meter (SC-2300, Suntex, Taiwan), and a potentiostat (CHI PVDF10

627D). The electrosorption unit cell consisted of a pair of carbon 1000 PVDF20
electrodes with a dimension of 80 mm  80 mm. The two PVDF30
3

oppositely planar electrodes were separated by a 2.0 mm spacer 800 PVDF40

for solution ow. The assembly of one half of the electrosorption
unit cell followed this sequence: Plexiglas cover, titanium plate, 600
carbon electrode, Viton gasket with hole, and central hollow
Plexiglas. In each experiment, the total solution volume was 35 ml 400
and the solution was continuously pumped by a peristaltic pump
with a ow rate of 7.2 ml/min. The variation of solution 200
conductivity was monitored at the outlet of the cell by using an
online conductivity meter. Thus, the NaCl solution concentration 0
can be obtained according to the linear relationship between 0.0 0.2 0.4 0.6 0.8 1.0
electrolyte concentration and conductivity, via a calibration table Relative Pressure (P/P0 )
made prior to experiment. Each experiment was performed until
the conductivity variation was not apparent to reach an equilibri- Fig. 2. Nitrogen adsorptiondesorption isotherms for activated carbon sheet
um state. Several electrosorption experiments under identical electrodes prepared by various contents of PVDF binder.
476 C.-H. Hou et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 473479

Fig. 3. SEM images for the PVDF10 electrode: (a) top view and (b) cross-sectional view, and for the PVDF40 electrode: (c) top view and (d) cross-sectional view.

Fig. 3(c) and (d), the surface of PVDF40 electrode is extensively

covered with polymer binder, meaning excessive amount of PVDF (a) 80 1st cycle 15th cycle
used to prepare the carbon electrode. Under this condition, the 5th cycle 20th cycle
Specific capacitance (F/g)

60
pores of activated carbon powders are blocked, leading to a 10th cycle 25th cycle
decrease of specic surface area of carbon electrode. 40

20
3.2. Electrochemical properties
0
The carbon sheet electrode prepared in this study was adding
hydrophobic PVDF as a polymer binder to x activated carbon -20
powders with strong mechanical strength in CDI process. However,
-40
the mixture of activated carbon powder and PVDF could (a)
accompany with strong hydrophobic property, which causes a -60
disadvantage to absorb water in electrosorption [18]. As shown in 0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6
Fig. 4(a), the cyclic voltammograms of PVDF10 for 1 M NaCl Applied potential vs. Ag/AgCl (V)
solution were repeated up to 25 cycles within a potential range of
0.60.4 V at 10 mV/s scan rate. One can see that the specic (b) 80 1st cycle 15th cycle
capacitance, related to the amount of ions electroadsorbed onto 5th cycle 20th cycle
Specific capacitance (F/g)

60
the electrode surface, steeply increases with the number of charge/ 10th cycle 25th cycle
discharge cycles. More importantly, the specic capacitance at 40
0.4 V in the rst cycle is 17.5 F/g, and then considerably increases
to 24.5, 41.8, and 51.0 F/g at the 5th, 15th, and 25th cycle, 20
respectively. It should be noted that the specic capacitance in the 0
rst cycle is only approximately 34% of the value in the 25th cycle.
In this case, the PVDF-bonded carbon electrode has poor pore -20
accessibility for ion electrosorption.
In order to enhance the hydrophilicity, the fabricated carbon -40
(b)
electrode was further treated in 1 M KOH for 24 h. Fig. 4(b) shows -60
the cyclic voltammograms for the KOH-treated PVDF10 electrode. 0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6
As seen, the PVDF10 has good electrochemical stability and its
Applied potential vs. Ag/AgCl (V)
specic capacitance reaches the same magnitude after several
cycles. For instance, the specic capacitance in the rst, 5th, 10th, Fig. 4. Cyclic voltammograms in 1 M NaCl solution with a scan rate of 10 mV/s for
15th and 20th cycle reaches 48.4, 50.9, 52.8, 54.1 and 55.2, (a) non-treated and (b) KOH-treated PVDF10 activated carbon sheet electrodes.

respectively. Moreover, the specic capacitance of the KOH-
treated carbon electrode in the 25th cycle is improved to 55.7 F/g,
which is relatively higher than that of the non-treated carbon
electrode. The result demonstrates that the pretreatment in KOH
solution could make the carbon electrode more favorable to absorb
water, as well as to increase the charge capacity.
To study the effect of PVDF content on electrochemical
properties of different fabricated carbon sheets, the cyclic
voltammetry and galvanostatic charge/discharge measurements
were performed in 1 M NaCl solution with a scan rate of 10 mV/s
and a current density of 0.1 A/g, respectively with the results
presented in Figs. 5(a) and (b). As observed, the PVDF10 shows a
typical double layer capacitive characteristic, in which the cyclic
voltammogram is a shape of rectangle without any redox reaction
peak and the charge/discharge curve is a well-trained triangular
shape presenting the linear voltage-time dependence. The feature
also suggests that the electrosorption charge/discharge is a
reversible process attributed to purely electrostatic interactions
[5,24]. However, as the PVDF content increases, the specic
capacitance of PVDF10, PVDF20, PVDF30, and PVDF40 correspond-
ingly decreases from 55.7, 49.4, 43.7 to 39.6 F/g at 0.4 V,
respectively. In addition, due to the excessive PVDF addition in
carbon electrode, the rectangular shape of cyclic voltammogram of
PVDF40 is distorted and the ohmic drop is observed in the charge/
discharge curve, indicating a considerable internal resistance.
Therefore, it should be emphasized that increasing the PVDF
content enhances the mechanical strength of carbon electrode, but
on the other hand, the addition of PVDF binder reduces the specic
capacitance and leads to a higher electrical or mass-transfer
resistance in electrosorption process.
(a) 80
PVDF10
(a)
Specific capacitance (F/g)
60 PVDF20
PVDF30
40 PVDF40
20
0
-20
-40
-60
0.8 0.6 0.4 0.2
Applied potential vs. Ag/AgCl (V)
(b) (b)
0.8
Voltage (V)
0.6
0.4
0.2
0.0
0 200 400
Time (s)
Fig. 5. (a) Cyclic voltammograms obtained a scan rate of 10 mV/s and (b)
galvanostatic charge/discharge curves with a current load of 0.1 A/g in 1 M NaCl
solution for activated carbon sheet electrodes fabricated with different PVDF
contents.
C.-H. Hou et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 473479 477
3.3. Electrosorption performance of capacitive deionization
Fig. 6 shows the electrosorption experiments using the non-
treated PVDF10, KOH-treated PVDF10, and PVDF40 as CDI
electrodes for a 0.002 M NaCl solution. The initial conductivity
was 245 ms/cm and the amplitude of applied potential was 1.2 V.
During charging process, an electric eld was applied between the
two carbon sheet electrodes, and thereby Na+ and Cl ions can be
electroadsorbed onto the oppositely charged electrode surfaces,
corresponding to a decrease of the solution conductivity. Table 1
lists the experimental results of electrosorption performance of the
PVDF10 and PVDF40 electrodes. One can see that the nal pH value
was increased within the range of pH 5.96.6. It demonstrates that
the concentration of H+ ions is maintained in NaCl solution, in
which no signicant electrolysis reaction of water take places in
electrosorption process. As shown in Fig. 6, when the non-treated
PVDF10 was used at 1.2 V, it shows that the conductivity of the
solution was reduced to 20 ms/cm for about 50 min. Additionally,
when the KOH-treated PVDF10 was used, a better electrosorption
performance was achieved and the conductivity signicantly
dropped to 8 ms/cm in electrosorption process. On the other hand,
for the PVDF40 electrode, the solution conductivity was only
reduced to 153 ms/cm after about 70 min. Furthermore, by using
Eq. (2), the electrosorption efciency for non-treated PVDF10,
KOH-treated PVDF10 and PVDF40 electrodes is 91.8%, 96.7% and
37.6%, respectively. The PVDF10 electrode with KOH-treatment
has the highest electrosorption efciency.
During discharging with a potential of 0.0 V, the solution
conductivity returns to about its initial value, meaning ions are
released from the double layer region back to the solution.
Furthermore, by converting the difference between the initial
conductivity and nal conductivity, the electrosorption capacity
(i.e., the amount of adsorbed ions forming electrical double layer
during charging) can be calculated according to Eq. (3). As a result,
when the PVDF10 electrode was treated in 1 M KOH solution, the
electrosorption capacity was improved from 42.3 mmol/g to
44.5 mmol/g. Also, the PVDF10 electrode has a much higher
electrosorption capacity (44.5 mmol/g) than that (17.3 mmol/g) of
the PVDF40 electrode. The ndings are consistent with the
electrosorption characteristics measured by the voltammetric
experiments. An electrode with a higher specic capacitance and
typical double layer capacitive characteristic has a better electro-
sorption performance.
Regeneration of carbon electrodes is a very important factor
affecting the practical use in CDI device. Fig. 7 shows the
0.0 -0.2 -0.4 -0.6
electrosorption/regeneration cycles of the PVDF10 electrode with
KOH-treatment, which was conducted by repeating several
PVDF10 Electrosorption (1.2 V) Desorption (0.0 V)
PVDF20 250
PVDF30
Conductivity(S/cm)
PVDF40
200
150
100
PVDF10
50 PVDF40
Non-treated
PVDF10
600 800 1000 1200 0
0 20 40 60 80 100 120
Time (min)
Fig. 6. Conductivity variation of 0.002 M NaCl solution with the operating time at
applied voltage of 1.2 V for non-treated PVDF10, KOH-treated PVDF10, and, PVDF40
carbon sheet electrodes.
478 C.-H. Hou et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 473479
Table 1
Experimental results of PVDF10 and PVDF40 activated carbon sheet electrodes.
Electrode Specic capacitancea (F/g)
PVDF10 55.7
Non-treated PVDF10 51.0
PVDF40 39.6
a
As measured by cyclic voltammetry at 10 mV/s.
b
Electrosorption experiments conducted in 0.002 M NaCl solution at 1.2 V.
250
Conductivity (S/cm)
200
150
100
50
0
Voltage (V)
1.2
0.8
0.4
0.0
0 40 80 120 160 200 240 280 320
Time (min)
Fig. 7. Multiple electrosorptiondesorption cycles of 0.002 M NaCl solution for
PVDF10 carbon sheet electrode upon the polarization and depolarization at 1.2 and
0.0 V, respectively.
charging (1.2 V) and discharging (0.0 V) processes in a 0.002 M
NaCl solution. When no oxidation and reduction reaction occurs in
electrosorption, the current mainly takes the reasonability for
charging the electrode to electroabsorb ions from the bulk solution.
As can be seen, the polarization of the PVDF10 electrode at 1.2 V
leads to a decrease of solution conductivity. At the same time, the
current rapidly increases to 0.035 A due to the migration of ions
onto the oppositely charged surface, and then continues to
gradually decrease until the electrical double layer is completely
formed at the electrode/electrolyte interface [25]. Furthermore,
the regeneration can be achieved upon the electrode depolariza-
tion at 0.0 V. As shown by the corresponding change in the solution
conductivity, the current is immediately turned to 0.006 A, and
then approaches about zero. It is noted that the same pattern can
be found in three repeated electrosorptiondesorption cycles. Also,
the decay of electrosorption capacity has not been observed. It
demonstrates that the electroadsorbed ions can be desorbed by
removing an electric eld, and then the carbon electrode can be
reused. Consequently, the electrosorption of ions using the
polymer-bonded carbon electrode is a reversible process that
the amount of electroadsorbed ions can be controlled, via
manipulation electrical double layer formation at the electrode/
electrolyte interface.
4. Conclusions
In this study, a nanoporous carbon sheet electrode has been
fabricated by mixing the activated carbon powder and PVDF
polymer binder. Increasing the PVDF content enhances the
mechanical strength of carbon electrode, but accompanies with
decreasing the specic surface area, double layer capacitance, and
electrosorption efciency. In addition, the electrosorption char-
Conductivity pH Removal efciencyb (%) Electrosorption capacityb (mmol/g)
(ms/cm)
Initial Final Initial Final
245 8 5.6 6.6 96.7 44.5
245 20 5.6 5.9 91.8 42.3
245 153 5.6 6.3 37.6 17.3
acteristics of the PVDF-bonded carbon electrode can be improved
by the KOH-pretreatment to increase its hydrophilic property. The
experimental results indicate that the PVDF10 electrode, compris-
ing 90% activated carbon powder and 10% PVDF binder, yields a
typical double layer capacitive behavior, associated with good
electrochemical characteristics for ion electrosorption. Based on
the results, the PVDF10 electrode has been proved to present a
good CDI performance in terms of electrosorption capacity and
reversibility of electrosorptiondesorption cycles of ions. Ions can
be effectively removed from aqueous solutions and the regenera-
0.04 tion of carbon electrode can be carried out by removing the applied
Current (A)
voltage. Therefore, the PVDF-bonded carbon sheet electrode would
0.02
be suitable for the application of ion electrosorption in CDI process
0.00 as well as in the commercial aspect. The ndings of this work can
contribute to developing electrosorption process for water
purication and desalination.
Acknowledgement
This work was partially nancially supported by the National
Science Council of Taiwan under Grant No. NSC-99-2218-E-029-
003.
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