Desalination 342 (2014) 315

Contents lists available at ScienceDirect

Desalination
journal homepage: www.elsevier.com/locate/desal

Application of Capacitive Deionisation in water desalination: A review

Faisal A. AlMarzooqi a,, Amal A. Al Ghaferi a, Irfan Saadat a, Nidal Hilal b
a
b

Masdar Institute of Science and Technology, PO Box 54224, Abu Dhabi, United Arab Emirates
Centre for Water Advanced Technologies and Environmental Research (CWATER), Swansea University, Swansea SA2 8PP, UK

H I G H L I G H T S

We review 180 years of breakthroughs and research in Capacitive Deionisation (CDI).

The critical deciency in CDI is the need of low cost/high efciency electrodes.
The CDI complex electrosorption process requires a comprehensive and robust model.
No comprehensive environmental assessment is done yet for CDI.
The CDI eld lacks long term reliability and operation, pilot scale demonstration.

a r t i c l e

i n f o

a b s t r a c t

Article history:
Received 23 November 2013
Received in revised form 20 February 2014
Accepted 24 February 2014
Available online 20 March 2014

This manuscript spans over 180 years of ideas, discoveries, inventions, breakthroughs and research in Capacitive
Deionisation (CDI) and Membrane CDI (MCDI) desalination. Starting with the rst discovery of the dissociation of
ions in solution under an electric eld by M. Faraday (1833), through the pioneering work of carbon aerogel ow
through capacitors by J. Farmer's group (1996) at Lawrence Livermore National Laboratory (LLNL), to the utilization of novel graphene and carbon nanotube (CNT) materials as electrodes, the CDI and MCDI technologies are
progressively making its path to the desalination industry. Through this review various deciencies of this technology have been identied, rst and far most was the need for low cost and efcient electrode materials. The
review identied that a low cost and high efciency electrode capable of processing high salinity (seawater)
stream still does not exists and is considered important if the technology is to make it to the industry. Furthermore, the lack of long term reliability, operation demonstrations and experience meant that information about
scaling and fouling are rather scarce. Taking a step further, no comprehensive environmental assessment such
as Life Cycle Assessment (LCA) or Environmental Impact Assessment (EIA) has been performed yet.
2014 Elsevier B.V. All rights reserved.

Keywords:
Desalination
Capacitive Deionisation
Membrane Capacitive Deionisation

Contents
1.
2.
3.
4.
5.
6.
7.
8.

Introduction . . . . . . . . . . .
Theory. . . . . . . . . . . . . .
Process modeling . . . . . . . . .
CDI patents development . . . . .
Membrane Capacitive Deionisation .
Electrode materials . . . . . . . .
Pilot scale CDI and MCDI . . . . .
Desalination energy . . . . . . . .

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4
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10
10

Abbreviations: ACF, Activate Carbon Fiber; AC, Activated Carbon; AMC, Activated Mesoporous Carbon; AEM, Anion-Exchange Membrane; BET, BrunauerEmmettTeller; CDI,
Capacitive Deionisation; CDT, Capacitive Deionisation Technology; CDC, Carbide Derived Carbon; CA, Carbon Aerogel; CC, Carbon Cloth; CNF, Carbon Nanober; CNT, Carbon Nanotube;
CEM, Cation-Exchange Membrane; DWNT, Double Walled Nanotubes; ED, Electrodialysis; EDR, Electrodialysis Reversal; EIA, Environmental Impact Assessment; FO, Forward Osmosis;
GO, Graphite Oxide; LLNL, Lawrence Livermore National Laboratory; LCA, Life Cycle Assessment; MCDI, Membrane Capacitive Deionisation; MC, Mesoporous Carbon; MED, Multi-Effect
Distillation; MSF, Multi-Stage Flash; OMC, Ordered Mesoporous Carbon; ppm, Parts Per Million; RF, Resorcinol Formaldehyde; RED, Reverse Electrodialysis; RO, Reverse Osmosis;
SWNT, Single Walled Nanotubes; VC, Vapor Compression; WHO, World Health Organisation.
Corresponding author. Tel.: +971 50 4749222.
E-mail address: falmarzooqi@masdar.ac.ae (F.A. AlMarzooqi).

http://dx.doi.org/10.1016/j.desal.2014.02.031
0011-9164/ 2014 Elsevier B.V. All rights reserved.

F.A. AlMarzooqi et al. / Desalination 342 (2014) 315

9.
Selectivity, sorption capacity and salt removal efciency
10.
Desalination cost . . . . . . . . . . . . . . . . . .
11.
Fouling and scaling . . . . . . . . . . . . . . . . .
12.
Environmental impact . . . . . . . . . . . . . . . .
13.
Research trends and conclusions . . . . . . . . . . .
Acknowledgment . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . .

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1. Introduction
There is no doubt that the global water shortage has led mankind to
energy intensive water extraction and treatment methods such as desalination. Brackish water and seawater desalination is one of the key strategic solutions to the ever increasing global water demand and ever
decreasing natural fresh water resources due to climate change and
unsustainable industrial depletion of natural fresh water resources.
Safe, simple, low cost and high capacity and recovery desalination technologies have always been the goal for scientists and engineers. Today
Reverse Osmosis (RO) membrane desalination, Electrodialysis (ED),
Multi-Effect Distillation (MED) desalination and Multi-Stage Flash
(MSF) desalination are by far the dominating technologies that are delivering fresh water to millions of people around the World. Alternative
less energy intensive technologies have always existed but never made
it to industrial deployment due to deciencies in cost and salinity limits,
one of these technologies is Capacitive Deionisation (CDI) and
Membrane CDI (MCDI).
Seawater and brackish water desalination have emerged to become
the strategic supply of water for many countries around the globe and
for the Arabian Gulf countries in particular. Through the past decades
technological advancement in MSF, MED and RO in particular commenced with great improvement in desalination cost reduction and increased ux and selectivity with reduced fouling. Consequently the
MSF, MED and RO technologies became the most widely used large
scale desalination techniques worldwide, while other technologies
ceased to compete due to deciencies in cost, efciency, scalability
and salinity. Currently the dominating desalination technology by capacity is RO (Fig. 1) with a share of 64% followed by MSF and MED
with a share of 23% and 8% respectively. The technology with the lowest
global desalination capacity is ED (4%) and CDI doesn't even come into
the picture here because it hasn't made it to full industrial scale yet.
This shows that CDI requires signicant development to be a competing

Other
1%

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11
11
12
12
12
13
13

and viable desalination technology with respect to the well-established

technologies RO, MED and MSF. This is a review on the potentials of the
CDI process and the developments this technology has undergone since
its early development stages to the most recent advancements.
The main factors hindering the CDI process from competing with RO,
MED and MSF are scalability, salinity, electrode efciencies and cost effectiveness [1,2]. One of the largest and most comprehensive tests using
the CDI technology (termed capacitive deionization technology, CDT)
was performed by T. J. Welgemoed and C.F. Schutte [3] where they demonstrated a 3785 m3/day CDI desalination unit. Typical RO desalination
plants have desalination capacities on the order of 100,000 m3/day.
Considering cost and salinity limits, their study also showed that CDI
can be cost effective against RO at low salinities. Furthermore, CDI can
only compete at higher salinities only if there is signicant enough
reduction in capital cost. Their results showed that for the case of
2000 parts per million (ppm) feed solution, the desalination cost for
RO was 0.35 $/m3 while that for CDI was 0.11 $/m3. In water softening
application, CDI has proven the ability to remove 85% of divalent ions
[4]. In the pharmaceutical industry, CDI has proven to be a good separation technique for the purication of insulin [5]. Microbial fuel cells have
also been integrated with CDI units as power sources for very low salinity feed [6,7]. Lab scale demonstrations have shown that in general the
CDI technology can assist in several separation processes [810].
Although successful implementation of the CDI technology in the seawater desalination has not been achieved yet, CDI has already found
its place in the brackish water desalination industry. One of the very
few manufacturers of CDI systems is Voltea, which had announced the
commercialization of a CDI technology back in 2012 [11] and released
this as the CapDI technology.
CDI desalination technology [13] is a member of the family of
electricity based desalination techniques also consisting from MCDI
[1416], ED [17,18], EDI [19,20] and electrodialysis reversal (EDR)
[21]. The concept of CDI stems from the two words capacitive and

ED (Electrodialysis)
4%

MED (Multi-effect
distillation)
8%

MSF (Multi-stage
flash)
23%
RO (Reverse
Osmosis)
64%

Fig. 1. Global desalination technologies share by capacity, adapted from Ref. [12].

F.A. AlMarzooqi et al. / Desalination 342 (2014) 315

+ + + + +
+ +
+
+ +
+
+
+
-

Brine

+ + +

Salt water

Desalinated
water

Salt water

+ + + + +
+ +
+
+
+

- - - - - - - -

- - - - - - - -

Electrode

Electrode

+ + + + + + + +

+ + + + + + + +
Electrode

Electrode

Fig. 2. Purication (a) and regeneration (b) processes in CDI.

deionisation. The term deionisation refers to the removal of charged

atoms or molecules in the form of ions and the term capacitive refers
to the fact that a capacitor is used to facilitate this removal. A capacitor
is a device made of one or more pairs of electrodes, oppositely charged.
An electric potential is applied to the electrodes producing positively
and negatively charged poles. Salt molecules dissolved in water exist
in the form of positively and negatively charged ions. Positive ions
(cations) are attracted by the electrostatic force to the negative electrode while the negative ions (anions) are attracted to the positive electrode. In this way ions are separated from the water solution. A cycle of
purication (ion removal, Fig. 2a) and regeneration (ion discharge,
Fig. 2b) is alternated to produce two streams of desalinated water and
brine, Fig. 2. It is important to note here that the potential difference
should not exceed the point at which the bonds in the water molecule
between the hydrogen atom and the oxygen atom breaks (known as
the Nernst voltage or the standard electrode potential of water, E
cell =
1.23 V) [22]. The potential difference across the electric double
layer shall not exceed 1.23 V. The potential difference across the cell,
might exceed the 1.23 V threshold to compensate for the circuit system
resistance and hence no hydrolysis happens in these cases [23]. The
threshold of Nernst voltage is specic to the local potential difference
experienced by the water molecules.
Experiments of electrochemical effects in a liquid environment date
back to the times of M. Faraday, when he reported in 18331834 that
the quantity of matter decomposed during an electrochemical decomposition process is proportional to the quantity of electricity passed
(1st law of Electrolysis) and that the mass of altered element at the electrode is proportional to the equivalent weight of that element (2nd law
of Electrolysis) [2427]. These ndings led to the development of the
rst law of Electrolysis,
mqc

where m is the mass of the substance separated at the electrode, q is the

total quantity of electric charge passed through and c is a constant
dened as
c

me
F

where me is the equivalent weight and F is Faraday's constant [28].

Research in this eld proceeded thereafter with accelerated development of patents starting during the early 1900s until today. Starting
in the year 1900, W. T. Gibbs proposed, through a patent, his electrolytic
apparatus with an intension to produce chlorates from water solutions
by exposing it to an electric current. Although the intension was different, this patent served as a starting point of the development of CDI
technology for water treatment. M. AlKuran in his PhD thesis [29]
presented a rather comprehensive review of patents based on the CDI
concept, starting with the rst patent by L. Dion in 1904 [30] to the
relatively more recent ones by J. Farmer et al. at LLNL in 1994. The
main advances in CDI during the 20th century came through the work
of D. D. Caudle's and S. Johnson's groups at the University of Oklahoma.

They were the rst group to propose the concept of ow-through capacitor system [31] and electrochemical demineralisation of water using
carbon electrodes in 1966 [32]. Y. Oren and A. Soffer later demonstrated
for the rst time a cyclic process for water desalination based on CDI
through the electrochemical parametric pumping [33,34]. This was
followed, in 1996, by the pioneering work of J. Farmer et al. at LLNL
where they used carbon aerogel electrodes in desalination [35].
The optimisation of the whole CDI process requires comprehensive
theoretical knowledge and robust process models to describe the sorption mechanism. Although several modeling attempts have been made,
the system still lacks a unied and robust model for process system optimisation [36]. S. Porada et al. in their comprehensive review in CDI
compiled the models available in literature to describe the phenomena
occurring in the CDI device. Integration of all these models into a single
unied one would lead to a more robust and complete description of the
process. This is an essential element for all further development in this
technology. Nevertheless signicant progress and developments have
been made especially in the area of electrode materials which gained
the largest interest within the research community and research in
this in particular acts as the driver towards the development of the industrial prototype version of CDI and MCDI, not neglecting the signicance and potentials of new innovative redesigns of the CDI concept.
2. Theory
To understand the theoretical background of CDI we take a stepback and look at the two desalination technologies which utilize electric
potential as a mean of salt separation, namely ED and CDI. The main
difference between ED and CDI lies in the ion separation mechanism.
In CDI the principal ion removal mechanism is through electrostatic adsorption by direct contact of electrodes with the solution. Hence in CDI,
ion transport is driven by electrostatic adsorption and not by oxidation
and reduction reactions [37]. Additionally it is believed that a Faradaic
reaction occurs between the electrode and dissolved components in
the feed solution. For example carbonyl and phenolic functional groups
on the carbon electrode can form chemical bonds with cations in
solution [38]. This contributes to the overall separation in the CDI cell.
As an electrochemical process which involves migration or adsorption of ions towards an electrode, the separation mechanism in CDI is
described by the double layer models proposed independently by H.
Helmholtz in 1883 [39] followed by J. Perrin in 1904 [40]. This concept
was rst identied by G. Quincke in 1861 [41] having two layers of
opposite charge at the interface, but the term double layer and else
known as Parallel-Plate model [42] was rst used by H. Helmholtz
later in 1883. H. Helmholtz and J. Perrin assumed that the electrode
will attract an oppositely charged layer of ions making a system of
two layers separated by a layer of water molecules known as the hydration sheath [42], for example if the electrode is negatively charged, a
negatively charged layer in the electrode and a positively charged
layer of ions in the solution make the double layer, Fig. 3.
By establishing an equivalence of a capacitor through this postulation of the electried interface, the capacitance electrostatic theory

F.A. AlMarzooqi et al. / Desalination 342 (2014) 315

Solution

qe -

+
+
+
+ qs
+
+
+

Water Solution

Potential (V)

Electrode

0
Length (m)

Electrode
-

Ions

Double-Layer

Ions

Interfacial Surface
Tension

Capacitor
Fig. 3. (left) The double layer model of H. Helmholtz and J. Parrin (qe and qs are charge densities of the electrode and solution respectively, qe = qs), (right) the potential prole with distance across the electrodesolution interface.

can be implemented on the double layers. Two important limitations

arise in this treatment of the HelmholtzPerrin model. First, the model
predicts constant capacitance i.e. the capacity doesn't change with the
potential difference, through the following relationship,
C

dq 0 A

dV
d

where q is the charge density, V is the potential difference, is the

dielectric constant of the solution, 0 is the free space permittivity, A is
the electrode surface area and d is the double layer thickness. The second limitation is that through this approach, one obtains a symmetrical
parabolic dependence of interfacial surface tension with the potential
difference,
max

0 AV 2
2d

where is the interfacial surface tension, A is the exposed electrode area

and V is the potential difference. Interfacial surface tension (Fig. 3) or

else called interfacial surface energy is a measure of the interfacial forces

between the bulk liquid and the electrode surface. By denition interfacial surface tension is the ratio of the change of work needed to change
the interfacial surface area over the change in surface area.
This dependence is else known as the electrocapillary curve and experimental measurements show asymmetrical parabola dependence,
Fig. 4. Consequently, the capacitance dependence on potential disqualies the theory of constant capacity with potential difference (Eq. (3))
and furthermore experimental data shows this variation, as shown in
Fig. 5.
To understand this effect, M. Gouy and D. L. Chapman independently
further developed the HelmholtzPerrin double layer model incorporating the gradient of electron density and the thermal effects leading
to the so-called Diffuse-Charge Model [44,45]. The use of a gradient of
electron density removes the discreetness of the parallel-plates analogy
and rather assumes a variation of electron density with distance at the
charged interface utilizing the ThomasFermi screening distance
[46,47]. The thermal effects are incorporated in the model by considering the Boltzmann constant k. Henceforth Eq. (3) evolved into Eq. (5)
(below) through the work of GouyChapman where they developed a
model expressing the capacity, C dependence on the potential difference M as


C

Fig. 4. Electrocapillary curve of different solutes Ref. [43].

v
!
u
2 2
ze0 M u
t 2 0 z e0 c0
cosh
2kT
kT

where z is an integer, e0 is the ionic-cloud charge, T is the temperature

and c0 is the concentration of ionic specie in solution [42].
Eq. (5) predicts a symmetrical inverted parabolic relationship between the capacity and potential difference due to the cosh function,
however experimental data of capacity vs. potential difference departs
from this symmetric nature of the proposed relationship, as shown in
Fig. 5(a) and this is more pronounced in Fig. 5(b). Upon closer examination these results show that the GouyChapman model only closely resembles the conditions of highly diluted systems such as the case for the
curve labeled 0.0, Fig. 5(a). These discrepancies can be partially attributed to the two main assumptions in the GouyChapman model, namely neglecting ionion interaction which becomes signicant at higher
concentrations, the assumption of point-charge ions; and assuming a
constant dielectric constant in the interface between the electrode and
the bulk solution [42].

F.A. AlMarzooqi et al. / Desalination 342 (2014) 315

Fig. 5. Capacity, C of mercury/solution interface against electrode potential Ec (a) for acetamideNaFwater system with 0.25 M NaF and varying amounts of acetamide 0.0, 0.25 and 2.53 M
(b) N,N-dimethylacetamideNa2SO4water system with 0.15 M Na2SO4 and varying of N,N-dimethylacetamide 0.00, 0.16 and 1.60 M Ref. [48].

Based on this, it was natural, to combine the models of Helmholtz

Perrin and GouyChapman into one, and this was achieved through
the work of Stern in 1924 [49]. The Stern model treats the system as
two capacitors in series with the total capacity expressed as,
1
1
1

C CH CG

where C is the total capacity and subscripts H and G denote the

HelmholtzPerrin and GouyChapman capacities respectively.
Close to the electrode, the capacity of HelmholtzPerrin dominates,
while towards the bulk solution the capacity of GouyChapman dominates. Similarly at high concentrations, CH CG, C CH while at low
concentrations, CH CG, C CG [42]. Nevertheless limitations still remain in the Stern model and it can be seen in the interaction between
the ions and the electrode. The Stern model assumes that the ions lay
in close proximity of the electrode but are not adsorbed, and this situation is only valid for ions such as Na+ and F in the NaF molecule.
Grahame showed that in such cases the Na+ and F ions are known
to be surrounded by a strongly attached hydration layer of water molecules which essentially stops the ions from chemically interacting with
the electrode [50]. Conversely in solutions with chloride ions Cl, these
ions chemically react with the electrode and the Stern model becomes
invalid.
3. Process modeling
Various research groups developed a series of models trying to emulate mainly the transport processes involved in the CDI cell
[15,33,34,38,5160]. Leading this eld at its early stages was the group
of J. Farmer at LLNL [61]. This eld still lacks a complete, comprehensive
and robust process model, especially for industrial applications where
inlet to outlet modeling of the system is required. The closest model analyzing the operation of CDI was developed by B. G. Jeon and H. C. No,
based on the PoissonNernstPlanck equation of electrostatics [54].
Most of the focus has been put into the ionic level modeling of the transport phenomena and very little effort has been put into the incorporation of these models into a more global process model that simulates a
complete CDI desalination module. Such models will open the door to
tackle optimisation problems in the areas of cell congurations, energy
recovery, temperature and pressure drops.

Based on the fundamental theory of double-layers in electrochemical engineering developed by HelmholtzPerrin, GouyChapman and
Stern, there have been efforts in modeling specic systems such as the
case in the electrosorption of ions with carbon aerogels and more generic models describing the transport phenomena within the proximity of
the electrodes. K. L. Yang et al. developed a model describing the
electrosorption of ions in carbon aerogel based on the double-layer theory [38]. It was shown through this model that there exists a cutoff pore
width wm, which puts a limit on the minimum pore size allowed. If the
pore width is smaller than the cutoff pore, overlapping of the electrical
double layer occurs and the capacitance characteristic is lost. In this case
the ions are not able to enter into the micropores and the carbon aerogel
losses its electrosorption capacity. K. L. Yang et al. dened the cutoff
pore width wm as



9
8
ed
>
>
>
>

1
e
exp
< d
=
2
2kT




ln
wm
>
>
e

d
>
: 8kT exp
;
1 >
2kT

where e is the electrical charge, d is the diffuse layer potential and is

the DebyeHckel parameter for a symmetrical 11 electrolyte dened
as
s
2
2NA Ie

kT

where NA is the Avogadro constant and I is the ionic strength. A characteristic of the cutoff pore is that it decreases with increasing concentration and the study found a value of ~ 0.6 nm for the specic case of
carbon aerogel. This model is valid for the cases of b0.1 M electrolyte solution and is case specic for cation responsive electrodes (e.g. carbon
aerogel). Other models estimated the cutoff pore to be smaller than
two Debye lengths [62] which overestimates the electrosorption
capacity of the electrode.An approach to model the CDI operation was
performed by B. G. Jeon and H. C. No [54] where they described the
cell-to-cell concentrations through the following equations,
C in;n1 C in;n

Npore;n Q pore;n
W RT;n

F.A. AlMarzooqi et al. / Desalination 342 (2014) 315

where Cin,n is the inlet concentration of the nth cell, Npore,n is the number
of pores, W is the volumetric owrate, RT,n is the retention time and
Qpore,n is the amount of cell removal by a single pore dened as
RT;n

10

where Cpore,n is the salt concentration increase inside a single pore and
Vpore is the pore volume.
The sensitivity analysis of the model developed in their work revealed results conrming that large pore depth (i.e. surface area) retention time and higher capacitance all lead to a better product water
quality. Further work on the development of such models will lead to
a more complete optimisation of the system taking into account cell
module conguration as well as all other process variables.
4. CDI patents development
Electrode material development started in the early 1990s with the
introduction of activated carbon material electrodes. M. D. Andelman
was amongst the rst to use such a material in this application, initially
through his patent on ow-through capacitors in 1990 [63]. One of the
major breakthroughs in CDI came through the pioneering work of J.
Farmer et al. at the LLNL during the early 1990s, when they used
novel carbon aerogel electrodes in a ow-through capacitor system in
1996 [35]. Their three consecutive patents served as a stepping stone
for most of the modern applications of the CDI technology [6466],
followed by one of their most recent development of the ow-through
electrode capacitive desalination system [67]. Development of electrode
material continued thereafter with the introduction of nanomaterial
such as CNTs with L. R. Shiue et al. amongst the rst to issue patents of
nanomaterial based electrodes in CDI systems in 2001 [68].
Another system-wise breakthrough was introduced to the CDI technology when M. Andelman and G. Walker proposed the use of charge
barriers within the cell through their patent on a Charge barrier owthrough capacitor in 2001 [69]. Soon this became the well-known
MCDI system through the developmental work of J. B. Lee et al. [70].
5. Membrane Capacitive Deionisation
CDI suffers a major problem during the regeneration step. This happens when the electrode is saturated with oppositely charged ions, at
this point, the purication step is stopped and regeneration is initiated
by opposing the sign of the electrode to start the desorption process of
ions from the electrode to the bulk uid. Unfortunately and naturally
once the electric potential on the electrode changes its polarity, it will
desorb the adsorbed ions but at the same time attract and adsorb the
oppositely charged ions from the bulk uid. In fact ion desorption and
adsorption occur simultaneously during this step. This causes incomplete regeneration of the electrode leading to depletion in its adsorption
capacity, and longer regeneration times and causes residual ion

- - - - - - - -

Electrode

Anion-exchange membrane

+
+

Brine

Salt water

Desalinated
water

Salt water

+
+ +

+ + + + +
+ +
+
+
+

Electrode

b
Cation-exchange membrane

Electrode
- - - - - - - -

C pore;n dt
0

Q pore;n V pore

accumulation blocking the way of other ions during the next

purication step. To overcome these problems MCDI is introduced
[1416,7075]. The concept of MCDI is a modication from the original
CDI technology with additional ion exchange membranes to assist in
preventing adsorption during the regeneration process. The cations
freely permeate through the cation-exchange membrane (CEM) towards the double-layer within the vicinity of the negative electrode
and the anions similarly permeate through the anion-exchange membrane (AEM) towards the positive electrode, Fig. 6. However during
the regeneration step and due to the existence of the CEM, anions cannot permeate through the membrane towards the now positive electrode and are held back in the bulk uid. Similarly cations on the
other side cannot permeate through the AEM. This rejection allows
complete regeneration of the electrode and exposure to the uid during
the purication step, Fig. 6. Tracking back this concept, J. B. Lee et al.
were the rst group to use the term MCDI system for such devices and
demonstrated in 2006 its use in processing power plant wastewater,
showing that the MCDI's sodium and chloride removal rate is 19%
higher than the case of CDI and the maximum salt removal is 92% at
an energy consumption rate of 1.96 kWh/m3 [70]. This energy consumption value is comparable to the range given in the proceeding
Table 1. However, it has to be noted that specic energy consumption
per cubic meter of desalinated water is a function of salinity. For example the energy demand values for MSF, MED and RO shown are for seawater salinity which is typically between 30,000 and 45,000 ppm while
the energy demand values for ED and CDI are for brackish salinity which
is typically b 10,000 ppm. In their study they used CEMs which are selectively permeable to cations between the negative electrode and the bulk
uid, and AEMs are used respectively in the opposite way.
Further studies on MCDI performed by H. Li et al. [71] using CNT and
carbon nanober (CNF) nanocomposite lms as electrodes showed
49.2% higher salt removal performance by MCDI compared to CDI. Furthermore they demonstrated that the performance of MCDI with a single pair of electrodes is comparable to a system of 10 electrode pairs in
CDI. Finally they conrmed that the existence of the ion-exchange
membranes had no inuence on the ion transport kinetics by showing
that the adsorption isotherms for MCDI and CDI both followed the I.
Langmuir [80] adsorption isotherm model. In another similar study Y.
J. Kim and J. H. Choi showed that depending on the operating conditions
(applied potential difference and owrate) there is an enhanced improvement of performance by 32.8%55.9% with MCDI in comparison
with CDI [81]. In removing other ions, Y. J. Kimetal showed that MCDI
can be used in the removal of nitrate ions as well as the sodium ions,
and the separation process can be controlled by changing the potential
difference applied to the cells [82]. A similar demonstration was performed by Y. J. Kim and J. H. Choi showing that a nitrate selective composite electrode can effectively remove nitrates from a solution using a
CDI unit [83].
The MCDI technology also holds potential in the energy recovery aspect. P. Dugocki and A. van der Wal [84] demonstrated that 83% of the
energy used to charge the capacitor can be recovered, comparatively an
energy recovery of 62.1% has been achieved with CDI units [85]. Energy

Fig. 6. Purication (a) and regeneration (b) processes in MCDI.

Electrode

F.A. AlMarzooqi et al. / Desalination 342 (2014) 315

Table 1
Approximate ranges of energy demands for various
desalination technologies, adapted from Refs. [3,37,51,7679].
Technology

Energy demand
(kWh/m3)

MSF
MED
RO
ED
CDI

1058
658
26
0.48.7
0.12.03

recovery in these systems refers to the energy recovered during the regeneration cycle; the current which is generated as a result of the release of ions from the electrode is withdrawn for the system to
recover some of the energy input. Further energy reduction can be
achieved through optimisation of the material and process. Material optimisation aims to use highly conductive electrodes and ion-exchange
membranes and to develop a fast charge and discharge kinetics electrode [84]. Similarly blending of different materials with the ion exchange membrane can further enhance the ion exchange capacity and
electrical conductivity as shown by the work of, N. S. Kwak et al. [86].
Concentration polarization and spacer shadow effect [87] both contribute to reduced electrosorption in CDI processes in general, Fig. 7.
Concentration polarization occurs due to the migration of ions towards
the double layer within the vicinity of the electrode, introducing a concentration gradient at the boundary layer which hinders ionic transport.
Spacer shadow effect also hinders ionic transport [88] due to the fact
that the spacer is nonconductive and can partly cover (shadow) the
membrane in the case of MCDI [84] and the electrode in the case of
CDI. To our knowledge, P. Dugocki and A. van der Wal are the only researchers who mentioned the shadow effect phenomena in the context
of MCDI and almost no effort has been made to reduce or eliminate this
adverse phenomenon within the MCDI eld. Conversely, research on reducing the effect of shadowing in the eld of Reverse ED (RED) gave
very promising energy recovery results [8995]. In fact P. Dugocki
et al. showed through the use of ion conductive spacers in the application of RED, a decrease in cell resistance by a factor of 2, an increase in
the power density by a factor of 3 and almost complete elimination of
the spacer shadow effect resistance [89]. Moreover, V. K. Shahi, S. K.
Thampy and R. Rangarajan [94] demonstrated that the current efciency doubled when conductive spacers are used. To a lesser extent J. Post
et al. demonstrated that decreasing the thickness of the compartments

also plays a role in increasing the power density [96]. To date, similar efforts in the eld of MCDI research has not been put, and based on the
promising results by P. Dugocki et al., V. K. Shahi, S.K. Thampy, R.
Rangarajan and J. Post et al. there is a signicant window for improvement in the energy optimisation of CDI and MCDI processes.
V. K. Shahi, S.K. Thampy and R. Rangarajan [94] showed evidence
that the use of conductive spacers suppressed concentration polarization. Other researchers also suggested similar results with the use of
ion conducting spacers [97]. However, concentration polarization still
exists even when conductive spacers are used and further optimisation
of the cell is required to reduce these effects.
To further enhance the performance, low resistance ion-exchange
membranes may also be implemented. P. Dugocki et al. studied the
effect of various process parameters on the ion exchange membrane resistance and revealed very important dependence results [98,99]. They
showed that the resistance had signicant dependence on NaCl concentration, inlet owrate and temperature. Below the threshold of b0.1 M
NaCl the resistance increased more than 5 times (Fig. 8) and this can signicantly affect the performance of the MCDI unit. Furthermore the
membrane resistance signicantly reduced by a factor of 34 when
the owrate was increased from 100 ml/min to 800 ml/min. Finally
the temperature sensitivity results showed a general decrease in resistance with temperature increase.
6. Electrode materials
It can be said that the majority of effort and focus in CDI and MCDI
research have been put into the development and synthesis of better
electrode materials. Numerous papers studied the various performances of different electrode materials with the abundance of carbon
based materials. The materials that have been investigated so far in literature are activated carbons [70,100118], alumina and silica nanocomposites [119], carbide derived carbons (CDCs) [111], carbon
aerogel [102,120126], CNTs and CNFs [71,101,102,127133], graphene
[127,134136] and mesoporous carbons [137]. Several authors also investigated the doping effects and blending of different materials on
the electrode performance [103,113,116,138148]. Fig. 9 below presents various electrode materials with their sorption capacity.
Activated carbon is a highly porous material synthesized through the
pyrolysis of carbon rich material such as coal and wood. J. Gamby et al.
studied different types of activated carbon electrodes and reported,

Spacer shadow effect

can be reduced by
conductive spacers
Electrode

CEM

Spacer

AEM

Electrode

In

Out

In
Concentration polarisation
is suppressed with
conductive spacers
Fig. 7. MCDI unit cell schematic with typical thicknesses of 300400 m for porous carbon
electrodes, 100130 m spacer, 100150 m CEM and AEM.

Fig. 8. Dependence of the ion exchange membrane resistance on NaCl concentration Ref. [98].

Sorption Capacity (mg NaCl/g electrode)

10

F.A. AlMarzooqi et al. / Desalination 342 (2014) 315

18.00
AC

16.00

ACF
ACF/CNF

14.00

AMC

12.00

CA

10.00

CC (woven)
CDC

8.00

CNT

6.00

CNT/CNF
GO

4.00

Graphene

2.00

MC

0.00

OMC

1996 2003 2005 2006 2008 2009 2010 2011 2012

Year
Fig. 9. A time-line for sorption capacity of various electrode materials, Activated Carbon
(AC), Activated Carbon Fibers (ACF), Carbon Nanobers (CNF), Activated Mesoporous
Carbon (AMC), Carbon Aerogel (CA), Carbon Cloth (CC), Carbide Derived Carbon (CDC),
Carbon Nanotube (CNT), Graphite Oxide (GO), Mesoporous Carbon (MC) and Ordered
Mesoporous Carbon (OMC) Refs. [35,81,101,106,111,113,128,132,134,137,149153].

specic surface areas of a range of 9202088 m2/g, median pore

diameter of 1.082.42 nm, resistance of 3.516.0 cm2, capacitance
of 60125 F/g and a total pore volume (b 50 nm) of 0.571.63 cm3/g
[154]. Activated carbon naturally has a hydrophobic characteristic
[103] and usually poly(vinylidene uoride) is used as a binder for the
activated carbon to maintain consistency in the material structure. Hydrophobicity of the electrode is undesirable since the electrode will
tend to repel the water solution reducing the degree of contact for sorption to take place. J. B. Lee et al. investigated this and found that the use
of ion exchange resins makes the electrode more hydrophilic [103]. I.
Villar et al. compared chemically activated carbon electrodes with carbon aerogel, carbon cloth, carbon felt and carbon paper electrodes and
concluded that activated carbon is the most suitable electrode material
since it exhibited higher surface area characteristic and suitable pore
size distribution [102].
L. Han et al. [119] investigated the use of alumina and silica nanoparticle coated electrodes and their results showed good electrode characteristics. Re-emphasizing the complexity of the electrosorption of ions
on porous material they point out the need to include the H+ and OH

concentrations in the sorption models. Furthermore, they indicate

the instability of the electrical double layer caused by thermal diffusion.
The electrodes had a specic surface area of 300 m2/g, pore size of
1.550 nm and specic capacitance of 18 F/g.
CDC electrodes have been investigated by S. Porada et al. due to its
pore size tunability at the sub-nanometer range [111]. In comparison
with activated carbon electrodes, CDC electrodes showed signicantly
higher salt adsorption capacity (28%44% increase). The CDC electrode
had a specic surface area of 5001250 m2/g, pore size of 0.72.0 nm
and specic total pore volume of 0.31 cm3/g.
Carbon aerogel has been the electrode of choice for many CDI and
MCDI applications including the pioneering patents by J. Farmer et al.
[6466]. In particular they exhibit superior electrical properties,
low electrical resistivity (b 40 m cm), high specic surface area
(4001100 m2/g) and controllable pore size distribution (b50 nm)
[120,155,156]. CNTs, CNFs and graphene electrodes are emerging materials gaining recent attention in the eld of CDI. With the increasing
number of publications on the use of these materials in CDI, patents
are already being led [157]. The specic surface area of graphene is estimated to be 2630 m2/g which is signicantly higher than that of activated carbons. In addition graphene and CNTs have high theoretical
conductivity exceeding 7200 S/m [127]. H. Li et al. compared the performance of these novel nanomaterial as electrodes in CDI application and
concluded that CNTs and Single Walled Nanotubes (SWNT) in particular

exhibited the highest electrosorption capacity in comparison to

graphene with values of 7.87, 9.35 and 12.79 mol/g for graphene, Double Walled Nanotubes (DWNT) and SWNT respectively. Furthermore
the actual measured surface area of the graphene, DWNT and SWNT
were 77,415 and 453 m2/g respectively which are much less than the
previously quoted gure (2630 m2/g). This huge discrepancy was attributed to the incomplete exfoliation and aggregation during the reduction process. Nevertheless there is a lot of room for development
in this area, especially with such novel nanomaterial having super physical, chemical and electrical properties.
L. Li et al. investigated ordered mesoporous carbon (OMC) electrodes in CDI [137]. Their work showed the potential of such material
in CDI and in particular it high specic surface area of 9501594 m2/g,
electrosorption capacity of 4.715.9 mol/g and specic capacitance of
these OMC electrodes was 108192 F/g depending on the preparation
method. Lastly, few other groups investigated the blending of titania
and silica gel in carbon aerogel and activated carbon electrodes to enhance their performance [113,116,122,138]. Similarly, C. Tsouris et al.
showed that mesoporous carbon based electrodes had superior salt
sorption capacity in comparison with carbon aerogel based electrodes
with a performance difference by a factor of 3. Moreover the mesoporous carbon based electrodes showed good salt sorption capacity of
21 mg of salts per gram of carbon for seawater at 35,000 ppm [150].
7. Pilot scale CDI and MCDI
Despite the fact that almost two decades have passed since the
pioneering work of J. Farmer et al. [35], the pilot and semi-pilot demonstrations of both the CDI and MCDI technologies have been rather
scarce. To our knowledge there have been only four pilot demonstrations of the CDI technology [3,126,158,159] with the highest owrate
at 3785 m3/day [3] and only one pilot demonstration of MCDI by P. M.
Biesheuvel and A. van der Wal at a peak owrate of 5.04 m3/day [15].
In general the pilot scale studies identied several factors which need
to be optimized and developed to take the CDI and MCDI technologies to
industrial level. So far carbon aerogel electrode based CDI can be competitive against RO, only for low salinity feed of 2000 ppm with a cost of
0.11 $/m3 for CDI and 0.35 $/m3 for RO. Furthermore CDI can reduce
the energy requirement of brackish water desalination from the typical
2.03 kWh/m3 value by RED to 0.59 kWh/m3, giving an energy saving of
70% [3]. At seawater concentrations of ~35,000 ppm RO remains more
cost effective and the cost of CDI needs to be signicantly reduced to
compete. Use of less expensive material with enhancement of energy recovery may potentially lead to reducing the cost. Scalability is an integral
part in any technology and in the context of CDI and MCDI, one needs to
consider the scalability of the manufacturing processes of the electrodes,
ion exchange membranes and spacers as well as the scalability of the actual process in terms of stacks and modules. T. J. Welgemoed and C.F.
Schutte successfully showed that carbon aerogel electrodes can be cost
effectively manufactured in a large scale [3]. M. Mossad and L. Zou
studied the effect of temperature, owrate and feed concentration
on the performance of a pilot CDI unit based on activated carbon electrodes [158]. They showed that there was an 11.2% (90.4% to 79.2%)
electrosorption efciency drop when the solution temperature was
increased from 20 to 50 C. Similarly increasing the owrate from 1 to
4.5 l/min led to a 28.4% (94.2% to 65.8%) electrosorption efciency
drop. Finally the increase in feed concentration from 500 ppm to 3500
ppm led to a 40.9% (95.3% to 54.4%) electrosorption efciency drop.
These results may suggest that the performance of CDI in a pilot scale
is highly dependent on feed concentration and relatively less sensitive
to feed owrate and temperature changes.
8. Desalination energy
The desalination of seawater and brackish water requires inputting
some form of energy either mechanical as in the case of pressure driven

F.A. AlMarzooqi et al. / Desalination 342 (2014) 315

desalination processes e.g. Nanoltration (NF) or RO, thermal as in the

case of MSF and MED, electrical as in the case of ED and CDI or
mechanical and thermal as in the case of Forward Osmosis (FO)
[160,161]. Regardless of the technology used, there exists a theoretical
thermodynamic minimum energy required for desalination which is
dependent on the concentrations of salts in the water (feed and product) and the water recovery i.e. the ratio of volume of desalinated
water to the volume of inlet seawater or brackish water. This minimum
is given by the equation [162]

0:296T
nout nin

nZout

log
nin

pa
p0

11

where W is the minimum energy (kWh/m3), T is the temperature (K),

nout and nin are the out and in molar concentrations, pa is the vapor pressure of the salty water (Pa) and p0 is the vapor pressure of pure water
(Pa).
For example the minimum required desalination energy for seawater at 35,000 ppm is approximately 1.09 kWh/m3 for a recovery of
50% while that for brackish water at 5000 ppm is 0.12 kWh/m3
[162,163]. In general the minimum required desalination energy
increases with concentration and recovery [13].
R. Semiat presented a wide range of energy demand values reported
from various references for MSF, MED and RO, expressing the diverse
numbers being quoted [162]. Similarly energy consumption values of
ED and CDI are collected from various references, Table 1. From the presented data in Table 1, it can be seen that CDI proves to be competitive
with RO, in consideration of the energy demand aspect. M. A. Anderson
et al. performed an extensive analysis of the energy demand in ED and
CDI, analyzing the effect of efciencies and various other parameters
on the energy consumption of each technology [13]. M. A. Anderson
demonstrated through this that even at moderate efciencies of
6070%, CDI is proven competitive. Furthermore, efciencies as high
as 92% and 95% have been achieved by R. Ktz and M. Carlen, and J. R.
Miller and A. F. Burke respectively [164,165]. S. Porada et al. presented
a comparison of the energy demand of RO and MCDI at different salinities [36]. There results showed that up to a salinity of 30 ppm, MCDI
proves very competitive with RO (Fig. 10). However, energy demand
is not the sole criteria for the success of a desalination technology. For
a desalination technology to be truly competitive and successful, all
technical, economic and environmental aspects should be considered
e.g. scalability, salinity limits, selectivity, cost, environmental impact etc.
9. Selectivity, sorption capacity and salt removal efciency
The selectivity and sorption capacity of various ionic species in
the feed water have been studied by various groups [100,124,126,
158,166]. In general the selectivity preference for cations followed

Fig. 10. Energy consumption of RO and MCDI at different salinities Ref. [36].

11

N I N Br N Cl N
Fe3 + N Ca2+ N Mg2+ N Na+ and for anions SO2
4
F N NO
3 . For the case of carbon aerogel electrodes C. J. Gabelich et al.
[124] and T. Y. Ying et al. [166] suggested that for the case having the
same concentration of ions in the feed solution the hydration radius determines selectivity. This was disproven by M. Mossad and L. Zou [158]
for the case of activated carbon electrodes. M. Mossad and L. Zou actually
showed that the selectivity dependence rather follows a hierarchy
starting rst with the charge afnity of the ion, having ions with higher
afnity more selectively adsorbed and then if the charge afnity is
equal, the hydration radius determines the selectivity. In terms of sorption capacity the general trend is, for cations Na+ Ca2+ N Mg2+ and
for anions Cl N Br N I. H. Li et al. further identied that the
electrosorption capacity in a solution with equal ion concentrations in
the feed can be an indicator to the selectivity of ions [167]. J. H. Lee,
W. S. Bae, and J. H. Choi also showed that the salt removal efciency
can be controlled by the applied potential and is increased by increasing
the potential [168]. Other references showed similar supporting results
[169]. In a different approach, J. K. Lee et al. showed through monoand bi-polar stacking, that the salt removal efciency is enhanced
when mono-polar stacking is used [170]. Through the use of activated
carbon electrodes, E. Avraham et al. demonstrated the ability to remove
30% of boron using CDI [171]. The typical boron concentration in seawater is 25 mg/l and the World Health Organisation (WHO) upper limit for
the concentration of boron in drinking water is 2.4 mg/l [172], therefore
the demonstration cannot meet the WHO requirement but it sets a
stepping stone for the boron separation technique in CDI.
10. Desalination cost
Desalination cost depends on many factors ranging from type of
technology, energy cost, feed water salinity, capacity and many other
site specic factors. I. C. Karagiannis and P. G. Soldatos carried out a rather comprehensive study on the cost of desalination, concentrating on
the well-established thermal (MED, MSF and Vapor Compression, VC)
and pressure (RO) driven desalination technologies [173]. Due to the
large number of variables impacting the desalination cost it's usually
difcult to give an absolutely fair comparison between the different
technologies. The desalination cost in CDI and MCDI has been looked
at by many authors in a range of ways through the use of low cost and
more efcient electrodes and ion exchange membranes and implementation of high energy recovery strategies [3,13,21,104,107,108,121,
122,126,135,138,174].
A direct comparison between CDI and RO was demonstrated by T. J.
Welgemoed and C.F. Schutte showing that for the case of small capacity
brackish water desalination pilot plants (3785 m3/day) the CDI technology gives a cost of 0.11 $/m3 while RO gives a cost of 0.35 $/m3 [3]. However other references show that for such small capacity, in brackish
units the cost range for RO falls down to 0.07 to 0.08 $/m3 [175]. The energy recovery and electrode material considered in T. J. Welgemoed and
C. F. Schutte's pilot demonstration were 50% to 70% and carbon aerogels
respectively. Henceforth there is a signicantly large window of improvement in the CDI and MCDI technologies with energy recoveries
approaching 98% and cheaper and more sorption efcient electrode material and ion exchange membranes. Through the improvement of the
manufacturing process of carbon aerogel electrodes, H. H. Jung et al.
[121] showed that Resorcinol Formaldehyde (RF) organic aerogels can
be cost effectively synthesized through ambient pressure drying instead
of supercritical drying [176,177]. Using the RF aerogels synthesized in
this way H. H. Jung et al. obtained removal efciencies on the order of
97.6%. Another approach was in the use of relatively cheap bipolar
graphite powder as electrodes in a packed bed, K. Dermentzis and
K. Ouzounis demonstrated that CDI can be carried out with removal efciencies of 76% to 85.6% [21]. The study lacks scale, since it was operating in a laboratory at very low owrates, 4.5 103 m3/day. L.M. Chang
et al. also showed the potential of using Activated Carbon loaded Titania
(AC-TiO2) as an electrode with a high desalination and desorption ratio

12

F.A. AlMarzooqi et al. / Desalination 342 (2014) 315

Table 2
Comparison of different electrode materials Ref. [138].
Electrode
material

Electrode cost
($/m2)

Desalination ratio
(%)

Desorption ratio
(%)

AC
AC-TiO2
ACF
CNT

0.89
1.07
2.97
450.01

27.5
44.9
13.8
51.6

67.3
89.8
55.9
44.6

in comparison with ACs and Activated Carbon Fiber (ACF) and lower
cost in comparison with ACF and CNTs. Table 2 below compares some
of the typical electrodes used in the CDI system in terms of their cost
and desalination/desorption performance. The area associated with
the cost is the BrunauerEmmettTeller (BET) surface area of electrodes. The desalination and desorption ratios are dened as follows:
desalination ratio

ni n f jadsorption equilibrium
ni

 100%

performance, indicating the increasing degree of fouling by organic

compounds. Another nding was that Ca2+ and Mg2+ ions had no noticeable effect on the performance of the CDI operation, since the regeneration cycle's efciencies for these two ionic species were 99.3% and
99.5% respectively. However Fe3+ ferric ion showed signicant effects
on the performance of the CDI reducing the salt removal efciency by
7.4% (88.4% to 81%) indicating scale formation. The study also showed
the effective cleaning of organic foulant (humic acid) and inorganic
scalant (Fe3+ ions) by alkaline and acid solutions and their ability to recover the CDI performance. It would be benecial to carry out similar
studies on carbon aerogel electrode based CDI and MCDI units to assess
the effects of fouling and scaling on their performance. Moreover the
long term exposure effect of alkaline and acid solutions on activated carbon and carbon aerogel electrodes needs to be investigated. Another
type of fouling which is very rarely mentioned in CDI publications is
biofouling. Y. Oren discussed the potential adverse effect of biofouling
on the technology and clearly shows that not enough research is done
in this particular area [180].
12. Environmental impact

desorption ratio

n f jdesorption n f jadsorption equilibrium

ni

 100%

where ni is the initial number of moles, nf|adsorption equilibrium is the nal

number of moles at adsorption equilibrium and nf|desorption is the nal
number of moles after desorption.
Further work is required to demonstrate the practicality of such
promising electrodes. S. Dietz highlighted that the cost of carbon materials in the application of CDI and MCDI has fallen by a factor of ve with
an eight fold increase in efciency of these electrodes [174].
11. Fouling and scaling
Fouling and scaling have not been publicly/academically addressed
in the application of CDI until recently. First it's important to differentiate between fouling and scaling since they are signicantly different
phenomena usually leading to the same problems. Fouling can be
thought of as the settling of solids on a surface creating an extra layer
of electrical, thermal and/or physical resistance. Scaling is rather a different phenomenon involving a physico-chemical change which causes
crystallization, precipitation and/or solidication of components from
the solution onto the surface. A typical scaling component is calcium
carbonate. The terms fouling and scaling are interchangeably used in
the work involving CDI and MCDI and are not clearly differentiated. It
is also noteworthy that although both phenomena are rarely addressed
in CDI applications, scaling is almost neglected in this context. Perhaps
one of the reasons for this is because scaling is usually a relatively
slow process which can be noticed after long operations and since
there is a lack of results of long operations in CDI and MCDI, such phenomenon is rarely mentioned. Nevertheless several authors have identied fouling and scaling aspects of CDI and MCDI where fouling was
usually caused by organic compounds and scaling was caused by organic and inorganic compounds [159,178180]. In comparison with RO and
ED, fouling in CDI and MCDI is believed to be less pronounced due to the
existence of a regeneration stage which cleans the membranes and electrodes and hence prevents the build-up of concentrates [70].
One of the most comprehensive studies performed on fouling and
scaling in CDI was by M. Mossad and L. Zou where they used dissolved
organic and inorganic salts to study these phenomena on activated carbon electrodes [159]. They showed that for a solution with only NaCl
there was almost no change in the performance of the CDI unit with a
regeneration efciency of 99.9% for 30 h of continuous operation.
When humic acid is used as an organic foulant decline in efciencies
and owrate was noticed after 17 h of operation. As the humic acid concentration was increased there was a faster and more severe drop in the

As for almost all desalination technologies, CDI and MCDI suffer the
most generic environmental problem of the disposal of the brine solution. Nevertheless solutions for the treatment of the brine solution and
reduction of their environment effect have been proposed and implemented and the most simple method is through the use of evaporation
ponds [181]. Since CDI and MCDI are relatively low energy intensive
technologies (Table 1) the other environmental impacts would be within the manufacturing process of electrodes and ion exchange membrane
and their disposal strategy. To our knowledge, so far no comprehensive
LCA or EIA has been performed for either CDI or MCDI. In terms of
disposal, the expected lifetimes for electrodes and ion exchange membranes are reported to be 10 years and 10 to 15 years respectively
[3,76,182]. However, the closest match to environmental assessment
of the CDI technology was performed by Cohen, I. et al. and Bouhadana,
Y. et al. [183,184] where they studied the long term stability of the electrodes, addressing the oxidation of the positive electrode which leads to
signicant reduction of desalination capacity. The unique work of
Cohen, I. et al. and Bouhadana, Y. et al. sets the stepping stones for
further investigation in both long term stability and reliability of the
technology, and further more offers a basis for future environmental
assessments.
13. Research trends and conclusions
It has been more than 15 years since the pioneering work of
J. Farmer et al. [35] which shed light back to the CDI technology and
brought the motivations back to the research in this eld. Although
CDI and MCDI have shown practicality and cost effectiveness in
brackish water treatment, the technology still lacks the last step of
commercialisation in this respect. The introduction of the MCDI concept
gave re-assurance that the CDI technology holds huge potentials in the
desalination elds, if enough research effort is dedicated to it. With
the lowest energy consumption and largest energy recovery potential,
the CDI technology offers most of the characteristics required for making the best available technology for some-kind-of-water desalination.
However, the main persisting roadblocks of high electrode material
cost and low salinity limit have always stopped the CDI technology
from gaining the expected popularity in the desalination community.
Furthermore, the complexity of the electrosorption process of ions
onto the material led to the lack of having a comprehensive and robust
process model, which in return hinders scientists in this eld from
performing thorough optimisation of the process system. Carbon
aerogels have had 15 years of application and development and is
continuing to develop but is losing its momentum with time. At the
same time, novel nanomaterials such as graphene and CNTs are gaining

F.A. AlMarzooqi et al. / Desalination 342 (2014) 315

momentum in this eld with their extremely high specic surface area
and super electrical properties. However, research in the use of CNT
and graphene as CDI electrodes is still at its early stages and initial milestones such as synthesis and fabrication of high surface area graphene
and CNT CDI electrodes have not been achieved yet. Furthermore, the
eld lacks semi-pilot and pilot scale demonstrations of graphene and
CNT based CDI systems. Research in CDI still lacks several efforts in different directions. Only a semi-pilot scale demonstration of the MCDI has
been performed so far and no complete pilot scale demonstration has
been performed yet. Pilot scale demonstrations will provide information about scalability, desalination cost, and salinity limits and can
offer long term studies of important phenomena such as fouling, scaling
and electrode and ion exchange membrane degradation. Similarly comprehensive environmental assessments such as LCA and EIA have not
been performed for neither CDI nor MCDI. Processing high salinity
streams such as seawater (~35,000 ppm) is currently almost not considered within the context of CDI and MCDI, but it is believed that there is
plenty of room for re-design and innovation in the CDI concept and it is
expected that breakthroughs similar to that of J. Farmer et al. [35] are yet
to come, with the urging of climate change, droughts and water scarcity
across the globe.
Acknowledgment
The authors would like extend their appreciation and acknowledge
the continuous support of Masdar Institute through the provision of
facilities and funding for the desalination research projects.
References
[1] P. Zhou, G. Brown, B. Gu, Membrane and other treatment technologies pros and
cons, in: B. Gu, J. Coates (Eds.), Perchlorate, Springer, US, 2006, pp. 389404.
[2] S. Nadakatti, M. Tendulkar, M. Kadam, Use of mesoporous conductive carbon black
to enhance performance of activated carbon electrodes in capacitive deionization
technology, Desalination 268 (13) (2011) 182188.
[3] T.J. Welgemoed, C.F. Schutte, Capacitive Deionization Technology: an alternative
desalination solution, Desalination 183 (13) (2005) 327340.
[4] S.-J. Seo, et al., Investigation on removal of hardness ions by capacitive deionization
(CDI) for water softening applications, Water Res. 44 (7) (2010) 22672275.
[5] S.-M. Jung, J.-H. Choi, J.-H. Kim, Application of capacitive deionization (CDI) technology to insulin purication process, Sep. Purif. Technol. 98 (2012) 3135.
[6] L. Yuan, et al., Capacitive deionization coupled with microbial fuel cells to desalinate low-concentration salt water, Bioresour. Technol. 110 (2012) 735738.
[7] C. Feng, et al., A microbial fuel cell driven capacitive deionization technology for
removal of low level dissolved ions, Chemosphere 91 (5) (2013) 623628.
[8] S.-J. Kim, J.-H. Choi, J.-H. Kim, Removal of acetic acid and sulfuric acid from biomass
hydrolyzate using a lime additioncapacitive deionization (CDI) hybrid process,
Process Biochem. 47 (12) (2012) 20512057.
[9] C. Forrestal, et al., Microbial desalination cell with capacitive adsorption for ion
migration control, Bioresour. Technol. 120 (2012) 332336.
[10] R. Brosus, et al., Removal of total dissolved solids, nitrates and ammonium ions
from drinking water using charge-barrier capacitive deionisation, Desalination
249 (1) (2009) 217223.
[11] Voltea completes 4.5mn funding round, Filtr. Ind. Anal. (2) (2012) 3.
[12] DesalData, www.desaldata.com ([cited 2013 06-11-2013]; Available from).
[13] M.A. Anderson, A.L. Cudero, J. Palma, Capacitive deionization as an electrochemical
means of saving energy and delivering clean water. Comparison to present desalination practices: will it compete? Electrochim. Acta 55 (12) (2010) 38453856.
[14] J.-H. Lee, J.-H. Choi, The production of ultrapure water by membrane capacitive
deionization (MCDI) technology, J. Membr. Sci. 409410 (2012) 251256.
[15] P.M. Biesheuvel, A. van der Wal, Membrane capacitive deionization, J. Membr. Sci.
346 (2) (2010) 256262.
[16] H. Li, L. Zou, Ion-exchange membrane capacitive deionization: a new strategy for
brackish water desalination, Desalination 275 (13) (2011) 6266.
[17] M. Sadrzadeh, T. Mohammadi, Sea water desalination using electrodialysis,
Desalination 221 (13) (2008) 440447.
[18] H.-J. Lee, et al., Designing of an electrodialysis desalination plant, Desalination 142
(3) (2002) 267286.
[19] K. Dermentzis, Continuous electrodeionization through electrostatic shielding,
Electrochim. Acta 53 (6) (2008) 29532962.
[20] K.X. Xu, Study on desalination Process of Electrodeionization (EDI) and Removal of
Copper from Water with the EDI, Tianjin University (People's Republic of China),
Ann Arbor, 2003.
[21] K. Dermentzis, K. Ouzounis, Continuous capacitive deionizationelectrodialysis
reversal through electrostatic shielding for desalination and deionization of
water, Electrochim. Acta 53 (24) (2008) 71237130.

13

[22] P.A.A.J.D. Paula, Physical Chemistry, Ninth ed. Oxford University Press, Great
Britain, 2010.
[23] Y. Show, K. Imaizumi, Electric double layer capacitor with low series resistance
fabricated by carbon nanotube addition, Diam. Relat. Mater. 16 (47) (2007)
11541158.
[24] M. Faraday, Experimental researches in electricity. Third series, Philos. Trans. R.
Soc. Lond. 123 (1833) 2354.
[25] M. Faraday, Experimental researches in electricity. Sixth series, Philos. Trans. R. Soc.
Lond. 124 (1834) 5576.
[26] M. Faraday, Experimental researches in electricity. Eighth series, Philos. Trans. R.
Soc. Lond. 124 (1834) 425470.
[27] M. Faraday, Experimental researches in electricity. Seventh series, Philos. Trans. R.
Soc. Lond. 124 (1834) 77122.
[28] F.C. Strong, Faraday's laws in one equation, J. Chem. Educ. 38 (2) (1961) 98.
[29] M. ALKURAN, Power Supply Considerations for Capacitive Deionization Water
Purication Systems, Engineering, The City University of New York, US, 2009, p. 137.
[30] L. Dion, Apparatus for treating liquids Patent Number 820482, U.S.P. Ofce, Editor
1906: United States.
[31] B.B. Arnold, G.W. Murphy, Studies on the electrochemistry of carbon and
chemically-modied carbon surfaces, J. Phys. Chem. 65 (1) (1961) 135138.
[32] D.D. Caudle, et al., Electrochemical Demineralization of Water With Carbon
Electrodes, United States Department of the Interior and University of Oklahoma,
United States, 1966.
[33] Y. Oren, A. Soffer, Water desalting by means of electrochemical parametric
pumping, J. Appl. Electrochem. 13 (4) (1983) 473487.
[34] Y. Oren, A. Soffer, Water desalting by means of electrochemical parametric
pumping. II. Separation properties of a multistage column, J. Appl. Electrochem.
13 (4) (1983) 489505.
[35] Joseph C. Farmer, J.H.R., David V. Fix, Scott L. Thomson, Sherman C. May, Desalination
with Carbon Aerogel Electrodes, Lawrence Livermore National Laboratory and
Bechtel Technology and Consulting, California, United States, 1996.
[36] S. Porada, et al., Review on the science and technology of water desalination by
capacitive deionization, Prog. Mater. Sci. 58 (8) (2013) 13881442.
[37] J.C. Farmer, et al., Capacitive deionization of NaCl and NaNO3 solutions with carbon
aerogel electrodes, J. Electrochem. Soc. 143 (1) (1996) 159169.
[38] K.-L. Yang, et al., Electrosorption of ions from aqueous solutions by carbon aerogel:
an electrical double-layer model, Langmuir 17 (6) (2001) 19611969.
[39] H.V. Helmholtz, Helmholtz's theory of double electric layers, J. Frankl. Inst. 115 (4)
(1883) 310.
[40] Perrin, J. Chim. Phys. 2 (1904) 601.
[41] G. Quincke, Ueber die Fortfhrung materieller Theilchen durch strmende
Elektricitt, Ann. Phys. 189 (8) (1861) 513598.
[42] John O'M Bockris, A.K.N.R., M.G.-A., Modern electrochemistry, Fundamentals of
Electrodics, Kluwer Academic Publishers, New York, 2000.
[43] F. Krger, H. Krumreich, ber die Gestalt der idealen Elektrokapillarkurve,
Z. Elektrochem. Angew. Phys. Chem. 19 (16) (1913) 617622.
[44] M. Gouy, Sur la constitution de la charge electrique a la surface d'un electrolyte,
J. Phys. Theor. Appl. 9 (1) (1910) 457468.
[45] D.L. Chapman, LI. A contribution to the theory of electrocapillarity, Lond. Edinb.
Dublin Philos. Mag. J. Sci. 25 (148) (1913) 475481.
[46] L.H. Thomas, The calculation of atomic elds, Math. Proc. Camb. Philos. Soc. 23 (05)
(1927) 542548.
[47] E. Fermi, Un metodo statistico per la determinazione di alcune priorieta dell'atome,
Rend. Accad. Naz. Lincei 6 (602607) (1927) 32.
[48] W.R. Fawcett, et al., Analysis of thermodynamic data for the adsorption of organic
molecules at polarizable interfaces with consideration of medium effects, J. Phys.
Chem. 92 (22) (1988) 63686373.
[49] O. Stern, Z. Elektrochem. Angew. Phys. Chem. 30 (1924) 508.
[50] D.C. Grahame, The electrical double layer and the theory of electrocapillarity,
Chem. Rev. 41 (3) (1947) 441501.
[51] P.M. Biesheuvel, M.Z. Bazant, Nonlinear dynamics of capacitive charging and
desalination by porous electrodes, Phys. Rev. E. 81 (3) (2010) 031502.
[52] P.M. Biesheuvel, B. van Limpt, A. van der Wal, Dynamic adsorption/desorption
process model for capacitive deionization, J. Phys. Chem. C 113 (14) (2009)
56365640.
[53] Z. Chen, et al., Kinetic and isotherm studies on the electrosorption of NaCl from
aqueous solutions by activated carbon electrodes, Desalination 267 (23) (2011)
239243.
[54] B.G. Jeon, H.C. No, Development of a two-dimensional coupled-implicit numerical
tool for analysis of the CDI operation, Desalination 288 (2012) 6671.
[55] R.A. Rica, et al., Thermodynamic relation between voltage-concentration dependence and salt adsorption in electrochemical cells, Phys. Rev. Lett. 109 (15)
(2012) 156103.
[56] J.-H. Ryu, et al., A study on modeling and simulation of capacitive deionization process for wastewater treatment, J. Taiwan Inst. Chem. Eng. 41 (4) (2010) 506511.
[57] R. Zhao, et al., Time-dependent ion selectivity in capacitive charging of porous
electrodes, J. Colloid Interface Sci. 384 (1) (2012) 3844.
[58] T. Humplik, et al., Nanostructured materials for water desalination, Nanotechnology
22 (29) (2011) 292001.
[59] P.M. Biesheuvel, Thermodynamic cycle analysis for capacitive deionization, J. Colloid
Interface Sci. 332 (1) (2009) 258264.
[60] B.G. Jeon, H.C. No, J.I. Lee, Development of a two-dimensional coupled-implicit
numerical tool for the optimal design of CDI electrodes, Desalination 274 (13)
(2011) 226236.
[61] J. C. Farmer, J.H.R., D.V. Fix, S. L. Thompson and S. C. May, U. Calif., 1996, Lawrence
Livermore National Laboratory.

14

F.A. AlMarzooqi et al. / Desalination 342 (2014) 315

[62] B. Corry, S. Kuyucak, S.H. Chung, Invalidity of continuum theories of electrolytes in

nanopores, Chem. Phys. Lett. 320 (12) (2000) 3541.
[63] M.D. Andelman, Flow-through capacitor Patent Number US5192432 A, U.S.P.
Ofce, Editor 1990: United States.
[64] J. Farmer, Method and apparatus for capacitive deionization, electrochemical
purication, and regeneration of electrodes Patent Number US5425858 A, U.S.P.
Ofce, Editor 1994: United States.
[65] J.C. Farmer, Method and apparatus for capacitive deionization and electrochemical
purication and regeneration of electrodes Patent Number US5954937 A, 1994:
United States.
[66] Tri D. Tran, J.C.F., Laura Murguia, Method and apparatus for capacitive deionization
and electrochemical purication and regeneration of electrodes Patent Number
US6309532 B1, 1994: United States.
[67] Matthew E. Suss, T.F.B., William L. Bourcier, Christopher Spadaccini, Michael
Stadermann, Klint Rose, Juan G. Santiago, Flow-through electrode capacitive
desalination Patent Number US20120273359 A1, 2012: United States.
[68] Lih-Ren Shiue, A.S., Chia-Chann Shiue, Fei-Chen Hsieh, Yu-His Hsieh, Jiung-Jau Jou,
Deionizers with energy recovery Patent Number US6580598 B2, U.S.P. Ofce,
Editor 2001: United States.
[69] M.A.A.G. Walker, CHARGE BARRIER FLOW-THROUGH CAPACITOR Patent Number
US20040174657 A1, 2001: United States.
[70] J.-B. Lee, et al., Desalination of a thermal power plant wastewater by membrane
capacitive deionization, Desalination 196 (13) (2006) 125134.
[71] H. Li, et al., Electrosorptive desalination by carbon nanotubes and nanobres
electrodes and ion-exchange membranes, Water Res. 42 (20) (2008) 49234928.
[72] Y.-J. Kim, J.-H. Choi, Improvement of desalination efciency in capacitive deionization using a carbon electrode coated with an ion-exchange polymer, Water Res. 44
(3) (2010) 990996.
[73] P.M. Biesheuvel, et al., Theory of membrane capacitive deionization including the
effect of the electrode pore space, J. Colloid Interface Sci. 360 (1) (2011) 239248.
[74] R. Zhao, et al., Optimization of salt adsorption rate in membrane capacitive
deionization, Water Res. 47 (5) (2013) 19411952.
[75] J.-Y. Lee, et al., Preparation of ion exchanger layered electrodes for advanced membrane capacitive deionization (MCDI), Water Res. 45 (17) (2011) 53755380.
[76] M. Turek, Cost effective electrodialytic seawater desalination, Desalination 153
(13) (2003) 371376.
[77] J.C. Farmer, et al., Capacitive deionization of NH4ClO4 solutions with carbon aerogel
electrodes, J. Appl. Electrochem. 26 (10) (1996) 10071018.
[78] Reverse Osmosis and Nanoltration, Manual of Water Supply Practices, M46,
(2nd Edition) American Water Works Association (AWWA), 1917.
[79] T.A. Peters, Desalination of seawater and brackish water with reverse osmosis and
the disc tube module DT, Desalination 123 (23) (1999) 149155.
[80] I. Langmuir, J. Am. Chem. Soc. 39 (1917) 1848.
[81] Y.-J. Kim, J.-H. Choi, Enhanced desalination efciency in capacitive deionization
with an ion-selective membrane, Sep. Purif. Technol. 71 (1) (2010) 7075.
[82] Y.-J. Kim, J.-H. Kim, J.-H. Choi, Selective removal of nitrate ions by controlling the
applied current in membrane capacitive deionization (MCDI), J. Membr. Sci. 429
(2013) 5257.
[83] Y.-J. Kim, J.-H. Choi, Selective removal of nitrate ion using a novel composite carbon
electrode in capacitive deionization, Water Res. 46 (18) (2012) 60336039.
[84] P. Dugocki, A. van der Wal, Energy recovery in membrane capacitive deionization, Environ. Sci. Technol. 47 (9) (2013) 49044910.
[85] O.N. Demirer, et al., Energetic performance optimization of a capacitive deionization system operating with transient cycles and brackish water, Desalination 314
(2013) 130138.
[86] N.-S. Kwak, et al., Synthesis and electrical properties of NaSSMAAMMA cation
exchange membranes for membrane capacitive deionization (MCDI), Desalination
285 (2012) 138146.
[87] H. Strathmann, Ion-exchange Membrane Separation Processes, Elsevier, Amsterdam,
Boston, 2004.
[88] J. Veerman, et al., Reducing power losses caused by ionic shortcut currents in reverse
electrodialysis stacks by a validated model, J. Membr. Sci. 310 (12) (2008) 418430.
[89] P. Dugocki, et al., Ion conductive spacers for increased power generation in
reverse electrodialysis, J. Membr. Sci. 347 (12) (2010) 101107.
[90] P. Dugoecki, et al., Practical potential of reverse electrodialysis as process for
sustainable energy generation, Environ. Sci. Technol. 43 (17) (2009) 68886894.
[91] D.A. Vermaas, M. Saakes, K. Nijmeijer, Power generation using proled membranes
in reverse electrodialysis, J. Membr. Sci. 385386 (2011) 234242.
[92] J. Balster, D.F. Stamatialis, M. Wessling, Membrane with integrated spacer, J. Membr.
Sci. 360 (12) (2010) 185189.
[93] E. Korngold, L. Aronov, O. Kedem, Novel ion-exchange spacer for improving
electrodialysis I. Reacted spacer, J. Membr. Sci. 138 (2) (1998) 165170.
[94] V.K. Shahi, S.K. Thampy, R. Rangarajan, The effect of conducting spacers on
transport properties of ion-exchange membranes in electrodriven separation,
Desalination 133 (3) (2001) 245258.
[95] K. Zhang, M. Wang, C. Gao, Ion conductive spacers for the energy-saving
production of the tartaric acid in bipolar membrane electrodialysis, J. Membr. Sci.
387388 (2012) 4853.
[96] J.W. Post, H.V.M. Hamelers, C.J.N. Buisman, Energy recovery from controlled mixing
salt and fresh water with a reverse electrodialysis system, Environ. Sci. Technol. 42
(15) (2008) 57855790.
[97] O. Kedem, Reduction of polarization in electrodialysis by ion-conducting spacers,
Desalination 16 (1) (1975) 105118.
[98] P. Dugocki, et al., On the resistances of membrane, diffusion boundary layer and
double layer in ion exchange membrane transport, J. Membr. Sci. 349 (12) (2010)
369379.

[99] P. Dugocki, et al., Transport limitations in ion exchange membranes at low salt
concentrations, J. Membr. Sci. 346 (1) (2010) 163171.
[100] C.-H. Hou, C.-Y. Huang, A comparative study of electrosorption selectivity of ions
by activated carbon electrodes in capacitive deionization, Desalination 314
(2013) 124129.
[101] G. Wang, et al., Hierarchical activated carbon nanober webs with tuned structure
fabricated by electrospinning for capacitive deionization, J. Mater. Chem. 22 (41)
(2012) 2181921823.
[102] I. Villar, et al., Carbon materials as electrodes for electrosorption of NaCl in aqueous
solutions, Adsorption 17 (3) (2011) 467471.
[103] J.-B. Lee, et al., Desalination performance of a carbon-based composite electrode,
Desalination 237 (13) (2009) 155161.
[104] K.-K. Park, et al., Development of a carbon sheet electrode for electrosorption
desalination, Desalination 206 (13) (2007) 8691.
[105] S. Porada, et al., Effect of electrode thickness variation on operation of capacitive
deionization, Electrochim. Acta 75 (2012) 148156.
[106] Y. Zhan, et al., Enhancement of electrosorption capacity of activated carbon bers
by grafting with carbon nanobers, Electrochim. Acta 56 (9) (2011) 31643169.
[107] J.-H. Choi, Fabrication of a carbon electrode using activated carbon powder and
application to the capacitive deionization process, Sep. Purif. Technol. 70 (3)
(2010) 362366.
[108] G. Wang, et al., Highly mesoporous activated carbon electrode for capacitive
deionization, Sep. Purif. Technol. 103 (2013) 216221.
[109] E. Avraham, et al., Limitations of charge efciency in capacitive deionization
processes III: the behavior of surface oxidized activated carbon electrodes,
Electrochim. Acta 56 (1) (2010) 441447.
[110] L. Zou, G. Morris, D. Qi, Using activated carbon electrode in electrosorptive
deionisation of brackish water, Desalination 225 (13) (2008) 329340.
[111] S. Porada, et al., Water desalination using capacitive deionization with microporous carbon electrodes, ACS Appl. Mater. Interfaces 4 (3) (2012) 11941199.
[112] M.T.Z. Myint, J. Dutta, Fabrication of zinc oxide nanorods modied activated carbon
cloth electrode for desalination of brackish water using capacitive deionization
approach, Desalination 305 (2012) 2430.
[113] M.-W. Ryoo, G. Seo, Improvement in capacitive deionization function of activated
carbon cloth by titania modication, Water Res. 37 (7) (2003) 15271534.
[114] H.-J. Oh, et al., Nanoporous activated carbon cloth for capacitive deionization of
aqueous solution, Thin Solid Films 515 (1) (2006) 220225.
[115] H.-J. Ahn, et al., Nanostructured carbon cloth electrode for desalination from
aqueous solutions, Mater. Sci. Eng. A 449451 (2007) 841845.
[116] M.-W. Ryoo, J.-H. Kim, G. Seo, Role of titania incorporated on activated carbon cloth
for capacitive deionization of NaCl solution, J. Colloid Interface Sci. 264 (2) (2003)
414419.
[117] P. Liang, et al., Coupling ion-exchangers with inexpensive activated carbon ber
electrodes to enhance the performance of capacitive deionization cells for domestic wastewater desalination, Water Res. 47 (7) (2013) 25232530.
[118] Z.-H. Huang, et al., Relation between the charge efciency of activated carbon ber
and its desalination performance, Langmuir 28 (11) (2012) 50795084.
[119] L. Han, et al., Mechanistic insights into the use of oxide nanoparticles coated
asymmetric electrodes for capacitive deionization, Electrochim. Acta 90 (2013)
573581.
[120] C.H. Hou, C.Y. Huang, C.Y. Hu, Application of capacitive deionization technology to
the removal of sodium chloride from aqueous solutions, Int. J. Environ. Sci. Technol.
10 (4) (2013) 753760.
[121] H.-H. Jung, et al., Capacitive deionization characteristics of nanostructured carbon
aerogel electrodes synthesized via ambient drying, Desalination 216 (13)
(2007) 377385.
[122] C.-M. Yang, et al., Capacitive deionization of NaCl solution with carbon aerogel
silicagel composite electrodes, Desalination 174 (2) (2005) 125133.
[123] R.W. Pekala, et al., Carbon aerogels for electrochemical applications, J. Non-Cryst.
Solids 225 (1998) 7480.
[124] C.J. Gabelich, T.D. Tran, I.H.M. Suffet, Electrosorption of inorganic salts from
aqueous solution using carbon aerogels, Environ. Sci. Technol. 36 (13) (2002)
30103019.
[125] J.C. Farmer, et al., The Use of Capacitive Deionization with Carbon Aerogel
Electrodes to Remove Inorganic Contaminants from Water, Lawrence Livermore
National Lab., CA (United States), 1995.
[126] P. Xu, et al., Treatment of brackish produced water using carbon aerogelbased capacitive deionization technology, Water Res. 42 (1011) (2008)
26052617.
[127] H. Li, et al., A comparative study on electrosorptive behavior of carbon nanotubes
and graphene for capacitive deionization, J. Electroanal. Chem. 653 (12) (2011)
4044.
[128] C. Nie, et al., Electrophoretic deposition of carbon nanotubes lm electrodes for
capacitive deionization, J. Electroanal. Chem. 666 (2012) 8588.
[129] C. Nie, et al., Electrophoretic deposition of carbon nanotubespolyacrylic acid
composite lm electrode for capacitive deionization, Electrochim. Acta 66 (2012)
106109.
[130] L. Pan, et al., Electrosorption of anions with carbon nanotube and nanobre
composite lm electrodes, Desalination 244 (13) (2009) 139143.
[131] H. Li, et al., Kinetics and thermodynamics study for electrosorption of NaCl onto
carbon nanotubes and carbon nanobers electrodes, Chem. Phys. Lett. 485 (13)
(2010) 161166.
[132] K. Dai, et al., NaCl adsorption in multi-walled carbon nanotubes, Mater. Lett. 59
(16) (2005) 19891992.
[133] C. Yan, L. Zou, R. Short, Single-walled carbon nanotubes and polyaniline composites for capacitive deionization, Desalination 290 (2012) 125129.

F.A. AlMarzooqi et al. / Desalination 342 (2014) 315

[134] Z. Wang, et al., Effective desalination by capacitive deionization with functional
graphene nanocomposite as novel electrode material, Desalination 299 (2012)
96102.
[135] B. Jia, L. Zou, Graphene nanosheets reduced by a multi-step process as highperformance electrode material for capacitive deionisation, Carbon 50 (6)
(2012) 23152321.
[136] B. Jia, L. Zou, Wettability and its inuence on graphene nanosheets as electrode
material for capacitive deionization, Chem. Phys. Lett. 548 (2012) 2328.
[137] L. Li, et al., Ordered mesoporous carbons synthesized by a modied solgel process
for electrosorptive removal of sodium chloride, Carbon 47 (3) (2009) 775781.
[138] L.M. Chang, X.Y. Duan, W. Liu, Preparation and electrosorption desalination
performance of activated carbon electrode with titania, Desalination 270 (13)
(2011) 285290.
[139] J. Yang, et al., Development of novel MnO2/nanoporous carbon composite
electrodes in capacitive deionization technology, Desalination 276 (13) (2011)
199206.
[140] Q. Liu, et al., Effect of dopants on the adsorbing performance of polypyrrole/
graphite electrodes for capacitive deionization process, Synth. Met. 162 (78)
(2012) 655661.
[141] Y. Zhang, et al., Polypyrrole nanowire modied graphite (PPy/G) electrode used in
capacitive deionization, Synth. Met. 160 (1314) (2010) 13921396.
[142] P.-I. Liu, et al., Microwave-assisted ionothermal synthesis of nanostructured
anatase titanium dioxide/activated carbon composite as electrode material for
capacitive deionization, Electrochim. Acta 96 (2013) 173179.
[143] B.-H. Park, J.-H. Choi, Improvement in the capacitance of a carbon electrode
prepared using water-soluble polymer binder for a capacitive deionization
application, Electrochim. Acta 55 (8) (2010) 28882893.
[144] J.-S. Kim, J.-H. Choi, Fabrication and characterization of a carbon electrode coated
with cation-exchange polymer for the membrane capacitive deionization applications, J. Membr. Sci. 355 (12) (2010) 8590.
[145] J.-Y. Choi, J.-H. Choi, A carbon electrode fabricated using a poly(vinylidene uoride)
binder controlled the Faradaic reaction of carbon powder, J. Ind. Eng. Chem. 16 (3)
(2010) 401405.
[146] B.-H. Park, et al., Capacitive deionization using a carbon electrode prepared with
water-soluble poly(vinyl alcohol) binder, J. Ind. Eng. Chem. 17 (4) (2011)
717722.
[147] K.C. Leonard, et al., Synthesis and characterization of asymmetric electrochemical
capacitive deionization materials using nanoporous silicon dioxide and magnesium doped aluminum oxide, Electrochim. Acta 54 (22) (2009) 52865291.
[148] Z. Peng, et al., Comparative electroadsorption study of mesoporous carbon
electrodes with various pore structures, J. Phys. Chem. C 115 (34) (2011)
1706817076.
[149] G. Wang, et al., Activated carbon nanober webs made by electrospinning for
capacitive deionization, Electrochim. Acta 69 (2012) 6570.
[150] C. Tsouris, et al., Mesoporous carbon for capacitive deionization of saline water,
Environ. Sci. Technol. 45 (23) (2011) 1024310249.
[151] P. Xu, et al., Treatment of brackish produced water using carbon aerogel-based
capacitive deionization technology, Water Res. 42 (10) (2008) 26052617.
[152] X. Wang, et al., Electrosorption of ions from aqueous solutions with carbon
nanotubes and nanobers composite lm electrodes, Appl. Phys. Lett. 89 (5)
(2006) 053127053127-3.
[153] L. Zou, et al., Using mesoporous carbon electrodes for brackish water desalination,
Water Res. 42 (89) (2008) 23402348.
[154] J. Gamby, et al., Studies and characterisations of various activated carbons used for
carbon/carbon supercapacitors, J. Power Sources 101 (1) (2001) 109116.
[155] E. Frackowiak, F. Bguin, Carbon materials for the electrochemical storage of
energy in capacitors, Carbon 39 (6) (2001) 937950.
[156] H. Prbstle, M. Wiener, J. Fricke, Carbon aerogels for electrochemical double layer
capacitors, J. Porous. Mater. 10 (4) (2003) 213222.
[157] John B. Stetson, J.M. Alan Rosenwinkel, Peter V. Bedworth, Perforated graphene
deionization or desalination Patent Number US 8361321 B2, 2010: United States.

15

[158] M. Mossad, L. Zou, A study of the capacitive deionisation performance under

various operational conditions, J. Hazard. Mater. 213214 (2012) 491497.
[159] M. Mossad, L. Zou, Study of fouling and scaling in capacitive deionisation by using
dissolved organic and inorganic salts, J. Hazard. Mater. 244245 (2013) 387393.
[160] R.L. McGinnis, M. Elimelech, Global challenges in energy and water supply: the
promise of engineered osmosis, Environ. Sci. Technol. 42 (23) (2008) 86258629.
[161] T.Y. Cath, A.E. Childress, M. Elimelech, Forward osmosis: principles, applications,
and recent developments, J. Membr. Sci. 281 (1) (2006) 7087.
[162] R. Semiat, Energy issues in desalination processes, Environ. Sci. Technol. 42 (22)
(2008) 81938201.
[163] K.S. Spiegler, Y.M. El-Sayed, The energetics of desalination processes, Desalination
134 (13) (2001) 109128.
[164] R. Ktz, M. Carlen, Principles and applications of electrochemical capacitors,
Electrochim. Acta 45 (1516) (2000) 24832498.
[165] J.R. Miller, A.F. Burke, Electrochemical capacitors: challenges and opportunities for
real-world applications, Electrochem. Soc. Interface 17 (1) (2008) 53.
[166] T.-Y. Ying, et al., Electrosorption of ions from aqueous solutions by nanostructured
carbon aerogel, J. Colloid Interface Sci. 250 (1) (2002) 1827.
[167] H. Li, et al., Using graphene nano-akes as electrodes to remove ferric ions by
capacitive deionization, Sep. Purif. Technol. 75 (1) (2010) 814.
[168] J.-H. Lee, W.-S. Bae, J.-H. Choi, Electrode reactions and adsorption/desorption
performance related to the applied potential in a capacitive deionization process,
Desalination 258 (13) (2010) 159163.
[169] E. Avraham, et al., Limitations of charge efciency in capacitive deionization II.
On the behavior of CDI cells comprising two activated carbon electrodes, J.
Electrochem. Soc. 156 (10) (2009) P157P162.
[170] J.K. Lee, et al., Comparable mono and bipolar connection of capacitive deionization
stack in NaCl treatment, J. Ind. Eng. Chem. 18 (2) (2012) 763766.
[171] E. Avraham, et al., The feasibility of boron removal from water by capacitive
deionization, Electrochim. Acta 56 (18) (2011) 63126317.
[172] W.H. Organization, Guidelines for Drinking-water Quality, Gutenberg, Switzerland,
2011.
[173] I.C. Karagiannis, P.G. Soldatos, Water desalination cost literature: review and
assessment, Desalination 223 (13) (2008) 448456.
[174] S. Dietz, Improved electrodes for capacitive deionization, Proceedings of the 2004
NSF Design, Service and Manufacturing Grantees and Research Conference
Birmingham, 2004.
[175] M.H.I. Dore, Forecasting the economic costs of desalination technology, Desalination
172 (3) (2005) 207214.
[176] S.J. Kim, S.W. Hwang, S.H. Hyun, Preparation of carbon aerogel electrodes for
supercapacitor and their electrochemical characteristics, J. Mater. Sci. 40 (3)
(2005) 725731.
[177] S.-W. Hwang, S.-H. Hyun, Capacitance control of carbon aerogel electrodes,
J. Non-Cryst. Solids 347 (13) (2004) 238245.
[178] Y.-J. Kim, et al., Desalination of brackish water containing oil compound by capacitive deionization process, Desalination 253 (13) (2010) 119123.
[179] L.Y. Lee, et al., Integrated pretreatment with capacitive deionization for reverse
osmosis reject recovery from water reclamation plant, Water Res. 43 (18)
(2009) 47694777.
[180] Y. Oren, Capacitive deionization (CDI) for desalination and water treatment past,
present and future (a review), Desalination 228 (13) (2008) 1029.
[181] M. Ahmed, et al., Use of evaporation ponds for brine disposal in desalination plants,
Desalination 130 (2) (2000) 155168.
[182] O.D. Savenko, F.T. Shostak, N.L. Boris, Synthesis of ion-exchange membranes, Russ.
Chem. Rev. 37 (11) (1968) 920.
[183] I. Cohen, et al., Long term stability of capacitive de-ionization processes for water
desalination: the challenge of positive electrodes corrosion, Electrochim. Acta
106 (2013) 91100.
[184] Y. Bouhadana, et al., Capacitive deionization of NaCl solutions at non-steady-state
conditions: inversion functionality of the carbon electrodes, J. Phys. Chem. C 115
(33) (2011) 1656716573