Electrochimica Acta 358 (2020) 136939

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Asymmetric electrode capacitive deionization for energy efficient

desalination
Esteban Toledo-Carrillo, Xingyan Zhang, Karthik Laxman, Joydeep Dutta∗
Functional Materials, Department of Applied Physics, School of Engineering Sciences, KTH Royal Institute of Technology, Hannes Alfvéns väg 12, Stockholm
114 19, Sweden

a r t i c l e i n f o a b s t r a c t

Article history: Capacitive deionization (CDI) is an emerging technology as a sustainable low energy process for desali-
Received 9 May 2020 nation of brackish water. Activated carbon electrodes are often used in the CDI devices. Electrosorption
Revised 6 August 2020
capacity was found to be improved on asymmetric electrode configuration using activated carbon cloth
Accepted 11 August 2020
doped with fluorine due to redistribution of electric potential. This led to improvement in desalination
Available online 14 August 2020
performance up to 12.4 mg/g for a desalination cycle of 6 min employing an asymmetric fluorinated
Keywords: electrode as cathode (ACC//F-ACC). A relatively high charge efficiency of 77 % was obtained representing
Capacitive deionization 92 % charge efficiency neglecting the leakage currents. Furthermore, the ion adsorption rate was found
Potential distribution to improve substantially due to an increased surface conductivity of the fluorinated electrode confirmed
Asymmetric electrodes by Mott-Schottky analysis. Energy consumption during desalination of 10 0 0 ppm sodium chloride solu-
Fluorine doping tion of 0.71kWh/m3 for symmetric electrode configuration was found to reduce by 36 % upon employing
Nitrogen doping
asymmetric configuration. This study shows some of the benefits of asymmetric configuration to achieve
an optimal operation of CDI device, as well as improvements related to energy consumption.
© 2020 The Author(s). Published by Elsevier Ltd.
This is an open access article under the CC BY license. (http://creativecommons.org/licenses/by/4.0/)

1. Introduction
Increase in water demands due to population growth and in-
dustrial requirements along with scarcity of freshwater resources
in many regions has become one of the primary global challenges
that need to be addressed. It has been reported that more than
half a billion people face drinking water shortages that is further
aggravated by the seasonal variations of water available for hu-
man consumption [1]. Thus, production of drinking water by de-
salination of alternative water sources such as brackish and sea-
water is of major interest to the scientific community as well as
the society. The challenges of fresh water production are being ad-
dressed through the desalination processes including reverse os-
mosis (RO) [2], multi-stage flash distillation (MSF) [3], nanofiltra-
tion (NF) [4] or electrodialysis [5]. However, most of these tech-
nologies are energy intensive and are often commercially not vi-
able compared to extraction of fresh water from ground or sur-
face water sources for meeting the drinking water requirements in
communities [6].
Capacitive deionization (CDI) is an emerging technology that is
showing considerable promises as a sustainable low energy pro-
∗
Corresponding author.
E-mail address: joydeep@kth.se (J. Dutta).
cess for producing potable water from brackish water. Its simplicity
and cost effective operation together with potential energy recov-
ery possibilities during its operation, makes it a promising technol-
ogy for addressing the increased drinking water needs [7,8]. A typ-
ical capacitive deionization device consists of two conductive elec-
trodes, separated by a spacer to provide electrical isolation of the
electrodes. The process of removing salt from brackish water con-
sist of two stages; namely, the desalination step, which is based
on the attraction and storage of ions (such as Cl− and Na+ ) on the
electrodes, through formation of an electrical double layer (EDL)
due to an applied electric field across the electrodes. The regener-
ation of the electrodes is done by either applying a lower voltage
than what was used for saturation of the electrodes, reversing the
polarity or simply short-circuiting the device while removing the
adsorbed ions from the electrodes.
High surface area, porous electrodes are generally used in ca-
pacitive device applications, as the large surface area allows the
formation of an EDL with a higher amount of ions stored [9].
Carbon based electrodes are mostly used in capacitive deioniza-
tion devices due to its inertness and the relatively lower costs of
production [10,11]. Carbon electrodes prepared in different forms
have been reported in the literature [12], e.g., as activated carbons
cloth [13], carbon xerogel [14], graphene-based electrodes [15],
single and multi-walled carbon nanotubes (SWCNT and MWCNT)

https://doi.org/10.1016/j.electacta.2020.136939
0013-4686/© 2020 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license. (http://creativecommons.org/licenses/by/4.0/)
2 E. Toledo-Carrillo, X. Zhang and K. Laxman et al. / Electrochimica Acta 358 (2020) 136939
[16] and more recently metal-organic framework-derived carbon
[17] amongst others.
Significant progress in improving the efficiency of desalination
has been made by modifying these electrode with either nega-
tively or positively charged functional groups like carboxylic or
amine groups (C=O, NH2 ) [18], coating with metal oxide nanopar-
ticles/nanostructures like zinc oxide (ZnO) [19-21], titanium diox-
ide (TiO2 ) [22], silica (SiO2 ) [23], manganese oxide (MnO2 ), etc
[24], by doping carbon with heteroatoms like nitrogen (N), boron
(B) or sulfur (S) [25,26] and intercalation materials such as MX-
ene [27], Prussian Blue and its analogues (PBA) [28]. Most of these
modifications improve electrode capacitance enhancing the elec-
trochemical properties leading to higher desalination capacities, or
by incorporating a pseudo-capacitive mechanism for salt removal.
Some of these techniques, like nitrogen doping at high temper-
atures, have been successfully implemented to increase the spe-
cific surface area, attributed to etching of the carbon materials
[29]. However, even with a large surface area and higher elec-
trode capacitance, a CDI device has to be operated at relatively
high potential (>1.0V) to reach charge efficiencies close to opti-
mum. Charge efficiency is defined as the ratio between the ad-
sorbed ionic species to the electronic charge provided to the elec-
trodes for attraction of the ions on its surface. In practice, the
charge efficiency is mostly governed by engineering design aspects
like external circuit resistances or contact resistances [30]; opera-
tional factor such as the ionic resistances due to solutions with low
ionic concentrations, or mechanistic factors, mainly related to the
phenomena of repulsion of ions with similarly charged electrode
(co-ions) are generally not considered. When the electrodes are
discharged during the regeneration phase (usually at V=0), elec-
trodes reach the short-circuit potential (E0 ) that is highly depen-
dent on the point of zero charge (Epzc ) of the electrode material,
wherein the net charge on the electrode is balanced by both anions
and cations adsorbed on its respective surfaces. However, when the
electrode is polarized away from the potential of zero charge dur-
ing the charging stage (ion adsorption upon application of an elec-
tric field), co-ions are repulsed (co-ion expulsion process) leading
to a loss of energy supplied in the device [31]. Thus it will be of
utmost importance to prevent co-ion expulsion in order to increase
the charge efficiency of capacitive deionization devices.
In this study a modified electrode configuration is proposed by
placing two electrode with different Epzc in an asymmetric elec-
trode configuration, so that during the discharging stage, the elec-
trodes are not allowed to reach the Epzc of either of the elec-
trodes, but both approaching the short-circuit potential positioned
away from the Epzc , so that the co-ions cannot be absorbed on
the same charge containing electrode. However, some disadvanta-
geous would arise when using asymmetric electrode configuration.
In theory, if an electrode is not chemically selective in the adsorp-
tion of an ionic specie, electrosorption should be symmetric either
by polarizing anodically or cathodically, which is not the usual case
when activated carbon electrodes are used [32]. However, by uti-
lizing an electrode with different chemical nature, the adsorption
process can be engineered to preferentially adsorb one of the ionic
species, leading to an uneven potential distribution. Since the sys-
tem is a closed circuit, there should be a charge balance across the
cell [33], which means that only one of the electrode adsorption
process would limit the desalination.
In this study, we demonstrate that asymmetric electrode config-
uration can be successfully implemented to balance the potential
distribution leading to an enhanced electrosorption capacity even
at relatively low operating potentials (0.8V). For this purpose, two
types of heteroatom-doped activated carbon electrodes were pre-
pared by fluorination (F-ACC) and nitrogenation (N-ACC), displac-
ing the Epzc from its initial point toward more positive or more
negative potentials, respectively. The optimization of the electrode
capacitance by tuning the nitrogen (N) or fluorine (F) content, cou-
pled with the suitable positioning of the electrode potential is
shown to increase the salt adsorption capacities, thereby improv-
ing the desalination efficiency of capacitive deionization devices.
2. Experimentals
2.1. Preparation of doped activated carbon cloth
Commercially procured activated carbon cloth (ACC) was em-
ployed as electrode base material (Zorflex FM10, Chemviron, UK).
ACC materials were first immersed in concentrated solutions of 3
M HNO3 at 80°C for 8 h to remove contaminants added during
manufacturing of these materials (like metal ions, organic matters
etc). ACC was then thoroughly washed with deionized water (DI)
and dried in an atmospheric oven at 90°C overnight, followed by
its storage in a desiccator until further use. Fluorine doped ACC
(F-ACC) was prepared by a chemical method in concentrated 20%
hydrofluoric (HF) acid solution at room temperature. Two pieces
of carbon cloth were immersed in HF solution and connected to a
power supply, with an applied voltage of 15 V for 20 min. Once
the external potential was removed, the samples were thoroughly
washed with DI water and oven dried at 90°C for 8 h in an atmo-
spheric furnace. In order to produce nitrogen doped ACC (N-ACC)
samples [34], 70 mg of dopamine hydrochloride (C8 H12 ClNO2 ) was
dissolved in 140 ml of 10mM Tris-hydrochloride (C4 H12 ClNO3 ) so-
lution. Then, previously cleaned ACC samples were dipped into
the solution followed by stirring for 8 h. The resultant ACC mate-
rial were thoroughly washed and dried following similar procedure
mentioned above, followed by a heat treatment at 800°C for 2 h in
nitrogen atmosphere.
2.2. Material characterization
Fourier transform infrared spectroscopy (FTIR, Nicolet iS10) in
attenuated total reflectance mode (ATR) was employed to charac-
terize surface functional groups in undoped and doped ACC. The
microstructure of the ACC samples were studied using a field emis-
sion scanning electron microscope, FE-SEM (ZEISS, Ultra 55). Nitro-
gen gas adsorption measurement was employed to calculate the
Brunauer-Emmet-Teller (BET) surface area (Micromeritics Gemini
VII).
2.3. Electrochemical characterization
Electrochemical measurements were conducted in a worksta-
tion using a Potentiostat/Galvanostat Gamry Interface 1010E with
a conventional three-electrode cell comprising of a platinum wire
as counter electrode, Ag/AgCl reference electrode and activated
carbon cloth samples as the working electrode. All the electro-
chemical measurements were carried out in aqueous solution of
0.5M sodium chloride (NaCl). Electrochemical Impedance Spec-
troscopy (EIS), which is an electrochemical technique to measure
the impedance of a system as a function of the frequency of the
AC signal, was performed within the frequency range from 100
kHz to 10 mHz. Complex impedance was also determined by scan-
ning a potential window between -0.8 to 0.8 VAg/AgCl at a fixed fre-
quency of 0.1 Hz. The capacitance values were calculated according
to Eq. (1).
 
 1 
C=  (1)
2π f Z 
where f corresponds to the frequency of the perturbation applied
and Z’’ is the imaginary part of the impedance. Similar proce-
dure was employed to study electronic properties by means of
Mott-Schottky analysis. The impedances were measured at 0.1Hz in
 E. Toledo-Carrillo, X. Zhang and K. Laxman et al. / Electrochimica Acta 358 (2020) 136939
aqueous solution of 0.1M potassium hydroxide (KOH). The CV mea-
surements were performed at different scan rates from 100 mV/s
to 1 mV/s. Specific capacitance of ACC and doped ACC were calcu-
lated based on CV measurement using Eq. (2) [35,36]:
 t
1
C= i dt
w V o
2.4. Desalination of brackish water
Desalination test were conducted in a CDI cell as shown in
Fig. S1 (Supporting information S1), in a flow-through architec-
ture. The experiments were performed in single-pass (continuous)
mode, using a non-deareated solution of 10 0 0 ppm NaCl, with a
flow rate of 5 ml/min. The pH of the solution was intermittently
measured thoroughout each cycle ranging from 5.9 to 6.1. The so-
lution conductivity was continuously monitored at the outlet tube
by a EPU357 eDAQ conductivity meter, and the current flow was
measured by a digital multi-meter Keithley 2110. The conductiv-
ity profile was not adjusted for pH fluctuations. During adsorption
step, an external potential was applied, which was swept between
0.8 to 1.4 V with a voltage step of 0.2V. For desorption, the cell
was self-discharged using 0 V across the electrodes. For further as-
sessment, a prolonged test of 25 cycles was performed at 1.0V and
1.6V.
For the analysis of the desalination performance, the specific
salt adsorption and charge efficiency were calculated using the fol-
lowing expression:
φ × ∫ (C0 − Ct )dt
=
m ACC
 ×F
=
M× 
where φ is volume flow rate (L/s), C0 refers to the constant influ-
ent concentration, Ct is the effluent concentration in each desalina-
tion cycle, t correspond to desalination time, m is the total mass of
both electrodes, F refers to Faraday constant, M is the molar mass
of NaCl and  correspond to the charge and is defined as the rate
between the absolute value of the current response during desali-
nation time to the mass of the electrodes.
3. Results and discussion
3.1. Physicochemical properties
Fig. 1 shows the FTIR spectra obtained from undoped ACC and
N and F doped ACC. Characteristic absorption at 3084, 1496, 1332,
1064 and 981 cm−1 assigned to O-H stretching, C=C stretching in
aromatic ring, O-H deformation, C-O stretching and C-O-C stretch-
ing vibrations, respectively can be observed in the ACC electrodes
[37–40]. Upon doping with nitrogen, two adsorption bands at 1318
and 1212 cm−1 , assigned to C=N and C-N stretching vibrations are
observed [41,42]. A pronounced and broader peak at 3075 cm−1 ,
related to N-H and O-H stretching vibrations also appear. Fluorina-
tion of the ACC electrodes, lead to the formation of C-F bonds in
the graphitic domain, giving rise to the appearance of a strong ad-
sorption band at ~1004 cm−1 from ionic C-F bond [40,43,44]. There
is a slight shift in the C=C peak position towards higher wavenum-
ber in both nitrogen and fluorine doped ACC samples, which might
be related to N/F insertion into the graphitic structure. It is im-
portant to note that the doped ACC spectra did not show any
pronounced adsorption peak for oxygen functional groups (~1600-
1750 cm−1 ), thus any major oxidation during either doping treat-
ment can be discarded.
Further analysis was carried out by observation of the morphol-
ogy and qualitative characterization of the chemical composition
3
(2)
Fig. 1. Attenuated total reflection FT-IR spectra of nitric acid treated ACC and nitro-
gen and fluorine doped ACC samples.
Table 1
Specific surface area (SSA) of
ACC and doped ACC measured
by nitrogen gas adsorption.
SSA (m2
(3) Sample /g)
± 10.04
1021.38
N-ACC 1014.81 ± 9.91
F-ACC 1059.10 ± 10.81
(4)
by FE-SEM and energy-dispersive X-ray (EDX) mapping, shown in
Fig. 2a–d. Both doped and undoped ACC samples exhibit a smooth
surface with no observable changes in fiber diameter, as earlier re-
ported for activated carbon fiber due to etching effects [45]. The
EDX mapping of N-ACC and F-ACC substrates shown in Fig. 2c,d
exhibit a significant homogeneous nitrogen/fluorine content on the
surface of the carbon fibers, respectively. Additionally, nitrogen gas
adsorption measurements were performed to quantify the specific
surface area (SSA) (Table 1). The undoped activated carbon elec-
trode exhibits a high specific surface area of ~1121 m2 g−1 . It has
been reported that doping treatment of activated carbon leads to
modification of the pore structure either by creating micropores
to increase the SSA, or alternatively reduction of the SSA was ob-
served due to widening of the existing pores [46]. However, neither
the N-ACC nor the F-ACC samples show any significant changes in
the surface area, which is in good agreement with the SEM obser-
vations.
3.2. Electrochemical properties
Cyclic voltammetry measurements were performed at different
scan rates to identify the contribution of pores of different sizes
and the surface charges. Fig. S2 a–f (Supporting information S2)
shows the cyclic voltammetry results at different voltage scan rates
ranging from 1 mV/s to 50 mV/s. Particularly, the voltammograms
corresponding to slower scan rates, display a distinctive quasi-
rectangular shape representative of an ideal capacitive behavior in
all the samples tested in this work. However, a pseudocapacitive
peak tend to form at higher anodic potential limiting the poten-
tial window for capacitive applications (above 0.8 V). This peak
is slightly more pronounced for N-ACC, related to an easier pro-
tonation of the surface. When the scan rate was increased up to
4 E. Toledo-Carrillo, X. Zhang and K. Laxman et al. / Electrochimica Acta 358 (2020) 136939
Fig. 2. Scanning electron micrographs (SEM) and energy-dispersive X-ray (EDX) mapping for (a,b) ACC (c) N-ACC and (d) F-ACC.
50 mV/s, a substantial loss of the rectangular shape, was observed
moving towards a lens-shaped progressive increment of the cur-
rent density for all the samples evaluated as shown in Fig. S2 a–
f (Supporting information S2). Based on the CV curves, the spe-
cific capacitance was calculated according to Eq. (2). A more de-
tailed analysis of the capacitive performance of the carbon elec-
trodes however, shows slight differences in the specific capacitance
of the doped activated carbon electrodes (Fig. 3 a,b). During both
the positive and negative polarizations, S-shaped curve for the spe-
cific capacitance is observed. It is a well-known behavior, which
relates to different pore size activation during electrosorption pro-
cesses [47]. Both curves present two plateau, one of them during
the fast scan rate and another in the slow scan rate domain. A fast
scanning of the voltage tends to generate an overlapped electrical
double layer blocking the entrance of the adsorbed ions into the
micropores, leading to ion adsorption occurring most likely in the
macropores. Conversely, when the voltage scan rate is lower, more
time is available for the ions to assemble into an electrical double
layer, allowing the ions to diffuse inside the smallest pores, leading
to a larger coverage of the total available surface area for adsorp-
tion. Thus, the double layer formed on the macropores would have
a negligible contribution to the capacitance of the electrodes ei-
ther for positive or negative polarizations as observed in the capac-
itance values at fast voltage scan rate. On the other hand, most of
the capacitance is related to the volume of micropores, thus lead-
ing to a specific capacitance of 193, 202 and 200 F/g for anodic
polarization and 222, 213 and 245 F/g for cathodic polarization for
ACC, N-ACC and F-ACC electrodes, respectively. A larger difference
in specific capacitance is identified in the cathodic side; with a 10
% increase in F-ACC and a 4% decrease for N-ACC in comparison to
undoped ACC. If the surface charge does not change after the dop-
ing treatments, then the specific capacitance differences for slow
voltage scan rates can be attributed uniquely to texture variations,
assuming that the entire surface area is covered with an electrical
double layer. However, F-ACC exhibit very little increment in the
SSA after doping treatment (~3 %). Besides, all the samples evalu-
ated in this work show a higher specific capacitance upon polar-
ization by negative potential, indicative of the nature of the sur-
face charge. Therefore, the large increment in capacitance can be
explained in terms of the electronegativity difference between the
C-F bond formed on the surface that shift the electrode potential
towards positive potential, allowing larger polarization in the same
potential window [36].
Fig. 4a shows the Nyquist plot of doped and undoped ACC from
experiments carried out in a 0.5M NaCl solution. The equivalent
circuit (Fig. 4b) proposed to fit the EIS curves, consist of four dis-
 E. Toledo-Carrillo, X. Zhang and K. Laxman et al. / Electrochimica Acta 358 (2020) 136939
Fig. 3. Specific capacitance calculated from CV curves at different scan rates for (a)
cathodic polarization and (b) anodic polarization.
Fig. 4. (a) Electrochemical Impedance Spectroscopy (EIS) curve for ACC samples in
0.5M NaCl (inset shows the open circuit potential before EIS) (b) Equivalent circuit
for EIS curves[50].
5
tinguishable stages, with an initial series resistance representative
of the ionic conductivity of the electrolyte (Rsol ), with a minor con-
tribution from the electrode conductivity. A second stage is rep-
resented by a semicircle in a Nyquist plot that correspond to an
RC combination associated to charge transfer process on the elec-
trode/electrolyte interface (Rct and CPE), and two final stages as-
cribed to the formation (Warburg component) and equilibrium ca-
pacitance (Ceq ), easily recognized by two different slopes in the
low frequency regime of a Nyquist representation [48–50].
A clear reduction in charge transfer resistance is observed after
doping treatment with either fluorine or nitrogen as reported in
some studies due to the addition of active sites by introduction of
heteroatoms in the graphitic structure [51]. Moreover, each sam-
ple shows a quasi-vertical slope in the low frequency range, cor-
roborating the capacitive behavior of the carbon electrodes, with
a marginal increase in the double layer formation time for F-ACC
electrode. By looking at the complex impedance value, it is possi-
ble to note that the equilibrium capacitance obtained by EIS mea-
surements (according Eq. (1)) increase in the following order CACC
< CN-ACC < CF-ACC .
The inset of Fig. 4a presents the open circuit potential (OCP)
measured prior to every EIS measurements wherein an increase of
about 150 mV for F-ACC was observed, similar to reports in previ-
ous studies [52], whereas N-ACC electrodes exhibit lower potential
than ACC. It should be noted that the initial state of ACC, prior to
fluorination or nitrogenation, oxygen functional groups are mainly
present on the surface, from the nitric acid treatment (Fig. 1) [53–
55]. This means that by the introduction of a C-N bond, a reduc-
tion in the electronegativity differences (with respect to C-O elec-
tronegativity difference) can be obtained which would simply be
the reverse in the case of C-F bonds. Further characterization by
determination of the potential of zero charge (Epzc ) of the elec-
trodes corroborate this argument.
Impedance measurements were carried out by sweeping the
potential at a fixed frequency of 0.1 Hz to provide enough time for
the electrical double layer formation. Thus, the capacitance values
were calculated according to Eq. (1), and normalized capacitance
values are shown found in Fig. 5a. The Epzc is determined where
the lowest capacitance value is reached, since a depletion regime
is achieved with no charge carrier accumulation on the electrodes
and thus the Epzc shown in Fig. 5a show a similar trend to open
circuit potential (Fig. 4a). The potential of zero charge plays an im-
portant role in CDI operation, since its position can limit the po-
tential window, or either enlarge or shrink the polarization level
of each electrode in a capacitive device [56]. Changes occurring
in an electrochemical interface as DC bias voltage is changed can
be characterized using Mott-Schottky analysis. The inverse of the
square capacitance is plotted as function of potential in a Mott
Schottky plot that allows the quantification of the density of charge
carrier according to the following expression (typically used to
characterize the potential difference between bulk semiconductor
and bulk electrolyte) (Eq. (5)) [57–59].
 
1 2 kT
= E − Efb (5)
C2 e0 εoε ND e
In Fig. 5b we present the Mott-Schottky plot, measured at 0.1
Hz in 0.1 M KOH aqueous solution for comparison. It is clear that
the base material already exhibit n-type doped surface, even be-
fore fluorine and nitrogen treatments. It is consistent with previ-
ous observation, since the carboxylic groups on activated carbon
cloth following the nitric acid treatment provides excess electrons
that lead to a n-type behavior with a low charge carrier concen-
tration due to formation of stable C-O bonds instead of C=O. Upon
fluorination, ACC shows an increase in charge carrier density, as
presented in Table 2 for F-ACC, due to the insertion of F atoms
on graphitic structure, inducing a larger amount of defects that
6 E. Toledo-Carrillo, X. Zhang and K. Laxman et al. / Electrochimica Acta 358 (2020) 136939

Fig. 5. (a) Normalized capacitance obtained from EIS at 0.1Hz (b) Mott-Schottky Fig. 6. Concentration profile for a desalination cycle in (a) symmetric configuration
plot at 0.1Hz in 0.1M KOH. at different voltage from 0.8 to 1.4V and (b) asymmetric configuration at 1.0V

Table 2
Charge carrier density (N) and flat band
potential (Efb ) calculated from Mott-
Schottky plot trosorption capacity, due to the charging potential, is related to the
15 −3
strengthening of the electric field that induces stronger columbic
Sample N x 10 (cm ) Efb (V)
force for the attraction of counterions [64]. The slope at the begin-
ACC 0.511 -0.006
N-ACC 4.023 -0.212 ning of the curve also suggests an increased ion removal rate, for
F-ACC 0.827 0.071 an increase in charging voltage.
Two new cell configurations were adopted replacing one of the
ACC electrodes, namely by N-ACC in the anodic side (N-ACC//ACC),
provides major number of lone pair electrons. Upon nitrogenation, while in another case by replacing the ACC electrode with F-ACC
the charge carrier concentration was even higher, which can be at- in the cathodic side (ACC//F-ACC). Each configuration was tested
tributed to a higher nitrogen content and due to the oxygen defects in the same external voltage range as for symmetric configuration,
induced due to the high temperature treatment that is consistent shown in Fig. S3 (Supporting information S3). A representative de-
with SEM-EDX mapping observations. In addition, the introduction salination cycle for CDI operation at 1.0 V is shown as a compari-
of nitrogen atom leads to incorporation of an excess electrons in son in Fig. 6b. It is clear that both asymmetric configurations lead
the graphite lattice for the most common type of bonding config- to an improvement of the desalination capacity as well as the ion
urations, increasing the carrier density of charge on the electrode removal rates, similar to what was achieved by increasing opera-
surfaces which compensate the reduction of electronic conductiv- tional potential for a symmetric electrode configuration. This im-
ity due to the defects formed [60–63]. provement can be related to the surface electrode conductivity in
heteroatoms doped carbon electrodes, as was proposed in previ-
3.3. CDI performance ous section, following the electrochemical measurements [64]. The
evolution of the desalination capacity and the charge storage ca-
Fig. 6a shows the concentration profile obtained from conduc- pacities of the electrodes were further studied by changing the
tivity measurement for an adsorption/desorption process employ- charging potential in the three device configurations. Fig. 7 (a,b)
ing a symmetric electrode configuration with ACC as both anode shows the specific salt adsorption and cumulative charge as func-
and cathode. The desalination test was performed at different ap- tion of the charging voltage. The ACC//ACC device exhibit a higher
plied potential ranging from 0.8 to 1.4V. Upon an increase in ap- charging potential dependency compared to the other asymmetric
plied potential, the reduction in ion concentration was more pro- ACC electrode configurations, with a very low salt removal yield
nounced, leading to a higher salt removal. This enhanced elec- ~3.5 mg g−1 at low applied potential (0.8 V).
 E. Toledo-Carrillo, X. Zhang and K. Laxman et al. / Electrochimica Acta 358 (2020) 136939
Fig. 7. (a) Specific salt adsorption (b) Cumulative charge as function of charging
voltage for the three different paring of electrode configurations.
The electrosorption capacity is linked to the electrode sur-
face area available for electrical double layer formation as well as
the capacitance of the electrode material as has been widely re-
ported [19,21]. Both of these electrode properties were character-
ized, showing negligible differences in the electrodes prepared for
this study. Nevertheless, a less studied feature, which influence the
electrosorption capacity, is the distribution of the applied potential
between the electrode, which in turn leads to uneven distribution
of the electrode capacitance [32,65]. As shown in Fig. S4 (Support-
ing information S4), a pair of electrodes were polarized at differ-
ent external potentials, measuring the working electrode potential
against a reference electrode Ag/AgCl. The working electrode po-
tentials are shown in Fig. 8a. For a “symmetric configuration”, the
polarization is larger in the cathodic side, as clearly noticeable in
Fig. 8b. This difference in the electrode polarization remain for all
the potentials applied (from 0.6 to 1.6 V). However, for an increas-
ing charging potential, the ratio between the cathodic and the an-
odic polarizations tend to decrease.
Some authors linked this uneven distribution to either chemical
interaction with ionic species that drive a selective electrosorption
or to pore size distribution that allows one of the ionic species to
diffuse easily inside the pore structure compared to the counterion
specie [31,33].
The two asymmetric electrode configurations show a more
even potential distribution. The ACC//F-ACC electrode configura-
tion presents a slightly more positive short-circuit potential (E0 ),
due to the position of the Epzc of F-ACC electrode; nonetheless the
electrode potential is shifted towards positive potential, allowing
7
Fig. 8. (a) Electrode potentials upon different polarization and (b) anodic and ca-
thodic polarization for symmetric and asymmetric configurations.
a more equal polarization. For N-ACC//ACC electrode configuration,
the working electrode potential shows the same trend as observed
in the symmetric ACC electrode configuration, but shows a larger
shift in E0 towards more negative potentials, providing a higher
polarization of the anode, which is the limiting factor for ion ad-
sorption. Thus, the electrode polarization (shown in Fig. 8a) ap-
proaches similar values for both the doped electrodes because af-
ter discharging the cell by short-circuiting (at E0 ), counter ions re-
main on the surface, as individual electrodes do not reach the po-
tential of zero charge (EPZC ). Thus, the ionic species on the surface
balances the surface charge on the electrodes, hindering the se-
lectivity of each electrode for the next desalination cycle. Thereby,
as the potential distribution is less dependent for both the asym-
metric electrode device configurations, the salt adsorption shows
similar trend. This strategy was evaluated for a prolonged oper-
ation of 25 cycles at 1.0V and 1.6V (Figs. 9 and 10). No change
is appreciable in the desalination performance after multiple cy-
cles of desalination/regeneration at 1.0V, without significant reduc-
tion in salt adsorption capacity for the three electrode configu-
ration studied in this work. Subsequently, a significant reduction
in salt adsorption (~ 15 %) for symmetric configuration and asym-
metric configuration comprising of ACC and F-ACC electrode, after
20 cycles is observed. The concentration profile for a single cycle
shown in Fig. 10 for each electrode configuration, reveals that both
the symmetric configuration and ACC//F-ACC electrode configura-
tion present an inversion peak at early stages of desalination after
25 desalination/regeneration cycles. This is associated to a degra-
dation of the anode, such as carbon oxidation [66], which might
8 E. Toledo-Carrillo, X. Zhang and K. Laxman et al. / Electrochimica Acta 358 (2020) 136939
Fig. 9. Concentration profile of a long-term desalination test at 1.0V of symmetric
(ACC//ACC) and asymmetric configuration (ACC//F-ACC and N-ACC//ACC).
be related to the use of pristine ACC electrode as anode in both
the cases. The N-ACC//ACC electrode configuration does not show
this behavior, allowing the desalination to occur in a larger poten-
tial window, since the electrode exposed to a high positive po-
tential in this case is the N-doped electrode, which is more re-
sistant to electrochemical oxidation. The energy consumed during
the desalination process remain approximately constant even after
25 cycles for all the three cases studied. However, 38 % less en-
ergy is required for desalination in both the asymmetric configura-
tions of the electrodes. It is important to note that for ACC//F-ACC
the potential window for CDI operations is limited at the anodic
Fig. 10. Concentration profile of a long-term desalination test at 1.6 V of symmetric (ACC//ACC) and asymmetric configuration (ACC//F-ACC and N-ACC//ACC).
side so that the potential should not surpass 0.8 VAg/AgCl , since
over this potential carbon electrode start to show evident degra-
dation for short-term operation [67,68]. Nevertheless, high poten-
tial operation is not necessary since low charging potential allows
higher salt adsorption compared to symmetric set-up. On the other
hand, by extrapolating the specific salt adsorption to a zero exter-
nal potential (Fig. 7a), one can notice that both N-ACC//ACC and
F-ACC//ACC fit perfectly to a linear trend, while in contrary, ACC
symmetric configurations cannot be associated to a linear expres-
sion, showing a clear deviation in the low voltage range. One has
to consider that during desalination, two simultaneous processes
occur, namely, the desorption of co-ions and adsorption of counte-
rions. This is usually related to a lowering in the charge efficiency
values, as presented in Fig. 11.
It has been proposed that to limit the desorption process during
desalination, a discharging potential higher than zero can be ap-
plied, so that during charging of the electrode, adsorption process
predominates [69]. However, this approach lead to a diminished
amount of salt removal. A well-established solution to this is the
addition of an ion exchange membrane, that avoid co-ion migra-
tion to the electrode surface, reducing the desorption process, but
it turns the CDI device to a more complex system. In retrospect,
asymmetric electrode configuration can reduce the co-ion repul-
sion during the desalination phase, since the initial working elec-
trode potential at this stage is already polarized from the Epzc , even
at a discharging potential of 0 V. It is important to note that the
aim of the present study is not to extend the voltage window by
shifting the potential of zero charge (since the regeneration stage is
conducted at zero voltage, instead of reversing the polarity to let
the electrode reach its lowest capacitance state), but to turn the
apparatus to a more efficient process [70].
The differences in charge efficiencies shown in Fig. 11 are in-
terrelated to mechanisms causing reduction in charge efficiency.
In symmetric configurations, a low efficiency is recorded at lower
 E. Toledo-Carrillo, X. Zhang and K. Laxman et al. / Electrochimica Acta 358 (2020) 136939
Fig. 11. Charge efficiency as function of charging voltage for the three different par-
ing of electrode configurations.
potentials because a significant amount of energy is wasted in
the process to repulse co-ions from the surroundings of the elec-
trode surfaces, while at higher potential the energy wasted is neg-
ligible compared to the energy effectively used to adsorb ionic
species. In case of asymmetric configurations, the co-ion repul-
sion is avoided to some extent, so the energy provided from low
potential is mainly used to attract ions, and as the potential in-
creases, the energy losses due to electrical and ionic resistances
becomes significant, leading to the higher potential drops, in ad-
dition to the leakage current from faradaic reactions [71]. Thus, a
highest charge efficiency of 77 % and 68 % at 0.8V was obtained
for F-ACC and N-ACC asymmetric cells, respectively. By neglecting
the leakage currents, a charge efficiency values of 92 % and 88 %
for both F-ACC and N-ACC asymmetric configuration respectively
were estimated, compared to a highest efficiency of 79% observed
for ACC symmetric electrode devices at 1.4V. From energy consid-
erations the results obtained in this work has broader implications,
since symmetric ACC electrode configuration would require energy
of ~0.71 kWh/m3 operating at 0.8 V. Even when the charge effi-
ciency increase substantially for ACC//ACC devices, the increase in
voltage requirements lead to higher power consumption. In con-
trast, both asymmetric electrode configurations show a lower en-
ergy consumption of 0.45 kWh/m3 at 0.8 V, which represents a
reduction of about ~ 36 % compared to the symmetric electrode
devices.
4. Conclusions
This work shows that the study of electrode potentials repre-
sents a key tool for the optimization of a capacitive deionization
device. Balance of the potential distribution lead to an enhanced
electrosorption capacity even at relatively lower operating poten-
tials (0.8 V) thereby improving the desalination efficiency of ca-
pacitive deionization devices. Asymmetric electrode configuration
with electrode of different Epzc wherein the electrodes are not al-
lowed to reach the Epzc of either of the electrodes during regen-
eration of the electrodes leads to lower co-ion adsorption on the
same charging containing electrodes. Equilibrium capacitance ob-
tained by CV measurements was 10 % higher in fluorine doped ACC
samples. The electrosorption in capacitors are widely linked to the
electrode surface area available for electrical double layer forma-
tion as well as the capacitance of the electrode material, but the
distribution of the applied potential between the electrode, which
9
in turn leads to uneven distribution of the electrode capacitance
is indeed another important aspect to be considered. It is demon-
strated that asymmetric electrode configuration can reduce co-ion
repulsion during the desalination phase, since the initial working
electrode potential at this stage is already polarized from the Epzc .
Charge efficiency values of 77 % and 68 % for both F-ACC and N-
ACC asymmetric configuration were reached at 0.8 V, respectively.
If the current leakage are neglected, charge efficiency of 92 % and
88% for F-ACC and N-ACC asymmetric cells were obtained, respec-
tively at 1.4 V applied potential, compared to a highest value of 79
% observed for ACC symmetric electrode device. This improvement
in charge efficiency leads to 36 % reduction of energy consumption
from 0.71 kWh/m3 for symmetric electrodes, to 0.45 kWh/m3 for a
CDI device working at 0.8 V. The obtained results suggest that dop-
ing activated carbon with heteroatom such as fluorine and nitrogen
leads to higher surface conductivity, responsible for enhancement
of ion removal rate, which is beneficial for shortening the deion-
ization cycles leading to better device efficiencies.
Credit author statement
E.T. performed the experiments, analyzed the data and wrote
the original manuscript. X.Z. assisted in the experiments. K.L. as-
sisted in the experiments and contributed to the discussion. J.D.
conceptualized the idea, supervised the experimental work and re-
vised and edited the manuscript.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgments
ET would like to thank to the National Commission for Scien-
tific and Technological Research, (CONICYT) for the Doctoral schol-
arship “Beca Chile” 2018-72190682. XZ would like to thank Ragnar
Holms Foundation for Post-doctoral fellowship. JD and KL would
like to acknowledge MISTRA Terraclean project (Diary No 2015/31)
for support.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.electacta.2020.136939.
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