Synthetic Metals 265 (2020) 116415

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Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet

Coconut shell-derived activated carbon and carbon nanotubes composite: a T

promising candidate for capacitive deionization electrode
Le Thanh Nguyen Huynha,1, Thi Nam Phamb,1, Thai Hoang Nguyena, Viet Hai Lea,**,
Thi Thom Nguyenb, Thi Diem Kieu Nguyena, Thanh Nhut Trana, Pham Anh Vu Hoa,
Thanh Thien Coa, Thi Thu Trang Nguyenb, Thi Kieu Anh Vob, Trung Huy Nguyenb, Thi Thu Vuc,
Viet Mui Luongd, Hiroshi Uyamad, Gia Vu Phamb,e, Thai Hoangb,e, Dai Lam Tranb,e,*
a
University of Science, VNU in Ho Chi Minh city, 227 Nguyen Van Cu, District 5, Ho Chi Minh City, Viet Nam
b
Institute for Tropical Technology, Vietnam Academy of Science and Technology, 18 Hoang Quoc Viet, Cau Giay, Ha Noi, Viet Nam
c
University of Science and Technology of Hanoi, Vietnam Academy of Science and Technology, 18 Hoang Quoc Viet, Cau Giay, Ha Noi, Viet Nam
d
Osaka University, Suita, Osaka 565-5871, Japan
e
Graduate University of Science and Technology, Vietnam Academy of Science and Technology, 18 Hoang Quoc Viet, Cau Giay, Ha Noi, Viet Nam

A R T I C LE I N FO A B S T R A C T

Keywords: Aiming at more efficient use of coconut resources to achieve multi-purpose goals, this work proposes an in-
Coconut shell novative composite for capacitive deionization (CDI) electrode in desalination applications when using coconut
Activated carbon (AC) shell-derived activated Carbon (AC) as a matrix into which a certain amount of carbon nanotubes (CNTs) is
AC-CNTs composite incorporated. The electrochemical studies show that the optimized 9mAC:1CNTs electrode with a surface area of
Capacitive deionization (CDI)
630 m2/g has a specific capacitance of 90.2 F/g (at scan rate of 20 mV/s), salt adsorption capacity (SAC) of 14.1
Desalination
mg/g at 1.0 V. SAC value is retained as high as 95.7% after 100 adsorption–desorption cycles at 1.0/0 V,
showing a good cyclic stability of the electrode composites. Moreover, a calculated specific energy consumption
(SEC) value of 0.312 kW h/m3 was quite low compared with other CDI electrodes reported in literature. Briefly,
the present study indicates that AC-CNTs composite can serve as promising CDI electrode materials for desali-
nation application.

1. Introduction
Effective water desalination at lower costs is presently considered as
one of the crucial technological challenges across the globe. Common
commercial technologies such as reverse osmosis (RO), electrodialysis
(ED), thermal distillation and multistage flash distillation have been
continuously developed to achieve higher efficient desalination.
However, high energy consumption levels of these technologies might
make them not truly feasible for water desalination in developing, still
poor countries in Asia, Latin America and Africa. In this context, ca-
pacitive deionization (CDI), based upon reversible salt ad-
sorption–desorption at porous carbon electrodes, becomes an alter-
native, cost effective technology, especially for brackish water
desalination [1–4]. Different carbon based materials such as activated
carbon (AC) [5–7], carbon nanotubes (CNTs) [8–10], nano-composite
[11,12], mesoporous carbons [13,14], carbon fiber [5,10], and recently
carbon aerogels [15] are intensively exploited in terms of CDI elec-
trodes. Among above listed carbon-based materials, AC is the most used
in CDI process study and commercialization due to its excellent prop-
erties (high surface area, tunable pore size distribution, variable surface
chemical composition) along with its abundance, low cost and scale up
production. The most common sources of AC on an industrial scale are
wood, anthracite and bitumen charcoal, lignite, peat shells and co-
conut. Alternatively, the use of sustainable biomass waste-derived
carbon has equally received much attention because they are of low
cost, environmentally friendly, easy to produce [2,16,17].
Having significant advantages, the development of CDI electrode
from AC confronts massive technological difficulties such as poor con-
ductivity, polydisperse size and pore distribution that lead to the poor
electrical characteristics of AC- based electrodes. Therefore, to improve

⁎
Corresponding author at: Institute for Tropical Technology, Vietnam Academy of Science and Technology, 18 Hoang Quoc Viet, Cau Giay, Ha Noi, Viet Nam. Tel.:
+844-38360538; Fax: +844-37564696.
⁎⁎
Corresponding author.
E-mail addresses: lvhai@hcmus.edu.vn (V.H. Le), tdlam@itt.vast.vn (D.L. Tran).
1
Both authors contributed equally to this work.

https://doi.org/10.1016/j.synthmet.2020.116415
Received 23 March 2020; Received in revised form 25 April 2020; Accepted 28 April 2020
0379-6779/ © 2020 Elsevier B.V. All rights reserved.
L.T.N. Huynh, et al.
their performance, certain amounts of conductive additives (carbon
black (CB), CNTs and graphene) are usually added to enhance final
electrical conductivity, improve electrochemical performance and
maximize their charge storage capacity of electrode materials
[5,18–21]. However, some issues should be addressed differently when
combining AC with one of the above additives. Notably, it was found
that CB could somewhat prevent electrolyte/ion transport to the ac-
cessible pores of AC and therefore lead to the poor functional perfor-
mance of CDI electrode. In other circumstance, inhomogeneous dis-
tribution of CNTs in AC (incompatible interaction between AC and
CNTs) due to the self- aggregation of CNTs can be predicted
[20,22–25].
In this study, we proposed a simple route to incorporate multi-
walled CNTs into coconut shell-based AC electrode. The rationale for
choosing AC as a starting material is provided by that coconut is ex-
tremely abundant in so called “coconut kingdom” Ben Tre province,
Mekong River Delta region of Viet Nam. Next, much more cost effective
and scalable production of multi-walled CNTs over single- walled CNTs
also make multi-walled CNTs more feasible for desalination application.
Further, the challenge of weak interaction between CNTs and AC can be
overcome by acid pretreatment for both starting AC and CNTs, enabling
the fabrication of homogeneous composites. The ratio of AC, CNTs and
binder in the composite is also well optimized to attain the most fa-
vorable ion transport upon reversible adsorption–desorption cy-
clability. Systematic studies of physico-chemical properties including
key parameters such as SAC, ASAR, and energy consumption have
shown the suitability of the as-obtained AC–CNTs composite used for
CDI electrode fabrication. Despite the starting materials to fabricate
these CDI electrodes may not be necessarily new, the ability to carry out
controllable and scalable manufacturing process for real, energy effi-
cient and robust CDI composite electrodes is unambiguously high-
lighted in this paper.
2. Experimental
2.1. Pre-treatment process of AC and CNTs
Activated carbon (AC) from coconut-shell (Figure S1) was provided
by Tra Bac company (TRABACO), Ben Tre province, Viet Nam with 30-
60 mesh sieve (0.25-0.50 mm); carbon nanotube (CNTs) was purchased
from NTherma Corporation (USA). The detailed pretreatment proce-
dure of AC and CNTs was included in supporting information (SI). All
characterizations of AC and CNTs were separately presented in Figures
S2- S10 of SI.
2.2. CDI electrode fabrication
To prepare the carbon slurry for coating process, mixture of treated
mAC (m denotes as “modified“), treated CNTs and poly(vinylidene
fluoride-co-hexafluoropropylene) PVF-HFP (Sigma-Aldrich) binder was
mixed with 1-methyl-2-pyrrolidinone (NMP, Sigma-Aldrich) solvent to
form a homogenous paste. The m-AC:CNTs mass ratio is varied as 9:1,
8:2 and 7:3. The graphite foils (Mineral Seal Corporation, USA) were
rinsed with ethanol and acetone for three times, dried at 100 °C for an
hour under vacuum. The carbon slurry was uniformly coated on the
Fig. 1. Schematic fabrication of mAC:CNTs/graphite electrode by doctor-blade method.
2
Synthetic Metals 265 (2020) 116415
graphite foil by drop casting method (“doctor blade” method) (Fig. 1).
The composite thickness was controlled to ca. 150 ± 10 μm. The
composite electrode maintains good mechanical properties and stability
after being immersed in NaCl solution in 30 minutes (Figure S11).
2.3. Morphological and electrochemical characterizations of CDI electrode
Composite morphology was observed using a field emission scan-
ning electron microscopy (SEM) by using JSM-6510LV instrument
coupled with Oxford EDX analysis system. Transmission Electron
Microscope (TEM) were performed on a JEM 2100 equipment (Jeol-
Japan). Brunauer-Emmett-Teller (BET) measurement under nitrogen
adsorption at 77 K was carried out with TriStar II-3000 analyzer
(Micromeritics-USA) to characterize surface area and pore structure.
Raman spectra were carried out on a LabRAM HR 800 Raman
Spectrometer (HORIBA Jobin Yvon) and collected in the wavelength
range of 900 – 1800 cm-1 at room temperature. The X-Ray diffraction
(XRD) patterns were taken with a D8-Advanced diffractometer
(Brucker) equipped with a LYNSEYES detector and CuKα radiation
(wavelength λ=1.5416 Å).
The electrochemical properties of mAC–CNTs composite were stu-
died by cyclic voltammetry (CV), Impedance Electrochemical
Spectroscopy (EIS) and the charge–discharge test. The CV was carried
out in the NaCl solution using a three-electrode system where the
working electrode, the counter electrode and the reference electrode
are prepared carbon electrode, platinum, Ag/AgCl (KCl saturated) re-
spectively. The CV measurements were performed in the potential
range of -0.5 V to + 0.5 V (vs. Ag/AgCl). The specific capacitance (Csp)
in F/g were calculated using the equation (1):
∫ IdE
Csp =
2 × m × v × ΔE (1)
Where ∫ I dE is the integrated area of the CV curve (A.V), and △V is
window voltage (V), ν is scan rate (V/s) and m is the mass active of
electrode material (g).
The AC impedance measurements were performed in the frequency
range of 105 to 10-3 Hz in open-circuit voltage with a potentiostat-
galvanostat VSP apparatus (Biologic). The excitation signal was 10 mV
peak to peak.
2.4. CDI performance
The CDI performance was conducted in a CDI batch-mode system
including a mono-cell CDI, a peristaltic pump, a conductivity meter and
a feed tank 50 mL, as illustrated in Fig. 2. The mono-cell CDI consists of
a pair symmetric mAC-CNTs/mAC-CNTs electrodes (size of 5 cm × 5
cm, thickness of 150 μm) separated by a polyamide spacer with a
thickness of 200 μm. The feed solution of NaCl (200 ppm and 1000
ppm) were circulated with a flowrate of 10 mL/min. The relationship
between conductivity and concentration was obtained from a calibra-
tion curve prior (Figure S11). The conductivity of NaCl solution was
acquired using an ion conductivity meter (Hanna). In CDI performance,
applied voltages at 1.0 V and 0.0 V (controlled by Autolab PGSTAT302
N (Metrohm)) were set for electro-adsorption and deadsorption re-
spectively. To calculate the salt adsorption capacity (SAC in mg/g) and
L.T.N. Huynh, et al.
Fig. 2. Schematic representation of CDI bath-mode system.
average salt adsorption rate (ASAR in mg/g.s), respectively, the fol-
lowing equations (2) and (3) are used:
Co − C
SAC = ×V
m (2)
SAC
ASAR =
t (3)
Where, Co and C are the initial and final concentrations of NaCl solution
(mg/L); m is the mass active of electrode material (g), V is volume of
NaCl (L) and t is time of desalination process (s).
3. Results and discussion
3.1. CDI electrode characterization
It is well known that Raman spectroscopy is an effective tool to
characterize the microstructure and bonding structure of carbon na-
nomaterials. Figure S2 presents Raman spectra of CNTs before and after
pre-treatment process, both showing two fingerprints, well-defined
peaks at 1324 cm-1 and 1576 cm-1, corresponding to the D-band and G-
band, respectively [26,27]. Theoretically, D-band exhibits the struc-
tural defect of the CNTs, relating to the functionalized surface of CNTs,
while the G-band indicates the graphitization and crystallinity of CNTs.
Thus, the relative ratio of the D-band and G-band (ID/IG) is proportional
to the degree of disorder in graphite structure. In our case, ID/IG ratio of
pristine CNTs and treated CNTs are 1.69 and 2.08, respectively. It can
be expected that the high ID/IG ratio signifies more structural disorders
and structural defects in the carbon framework of treated CNTs, thus
promoting the dispersion ability of CNTs in AC composite as well as the
ion accumulation and ion mobility in operational CDI systems
[20,28,29].
SEM/TEM images show that through the acid pretreatment, en-
tangled multi-walled CNTs became untangled, with a length from 0.5
up to 1 μm, a diameter of 20-30 nm. Since the CNTs length before and
after the treatment was not be significantly different, it can be implied
that pretreatment may contribute mainly in modifying functional
groups. Further validation of this assumption was IR data provided that
hydrophilic functional groups (–COOH, –OH) were generated on CNTs
surface. These additional groups of CNTs (and AC) certainly increase
dispersion stability of CNTs within AC matrix.
Briefly, Raman, SEM/TEM and IR data have demonstrated that the
acid pretreatment has been successful in terms of surface functionali-
zation while maintaining the precise parameter control of starting
CNTs, AC materials. The surface functionalization, it its turn, can ef-
fectively improve the dispersion of CNTs throughout mAC matrix and
thus improvee electrical conductivity of the mAC-CNTs composite. The
spectroscopic details were included in SI (Figures S3-S7).
3
Synthetic Metals 265 (2020) 116415
XRD patterns of mAC-CNTs composites shows a broad, strong peak
in 2θ range of 20°-30° and a much lower diffraction signal at ca. 44°.
The broad peak can be assigned to the disordered graphitic phase of
mAC while the tiny one can be attributed to the characteristic peak
(100) of CNTs [23,30]. It was observed that being embedded into mAC
matrix, the intense peak (002) at 2θ of ca. 26°, inherent in graphitic
structure of CNTs, becomes broader and weaker, possibly due to the
peak superimposition of the CNTs with a large band of the mAC. Thus,
XRD pattern supports the presence of CNTs and mAC in mAC-CNTs
composite. Fortunately, the disordered amorphous composite structure
can be an advantageous feature for electrochemical properties of CDI
electrodes (Figure S8).
SEM and TEM images of mAC-CNTs composites with different ratios
were presented in Figs. 3 and 4 respectively. It can be seen from these
figures that CNTs are highly elongated and interconnected with the AC
to form the condensed fibers with the voids. The interconnected voids
are further quantified by the specific surface area measurements
(Table 1). As discussed, despite a modest specific surface area of multi-
walled CNTs (110 m2/g, much lower to that of single-walled CNTs (ca.
1000 m2/g), however, cost effective and scalable availability of multi-
walled CNTs production made it more competitive over single walled
CNTs for the purpose of selecting economically feasible electrode ma-
terials for CDI desalination application.
The contact angle measurement is further used to determine the
degree of hydrophobicity (wettability) of mAC-CNTs composites. As it
can be seen from photograph of water droplets on mAC-CNTs surface,
the water contact angle was measured as high as 118 ± 3°, affirming
high hydrophobicity (low wettability) of the composites. Insignificant
change in contact angle, obtained with or without acid pretreatment
process as well as when varying CNTs amount in composite means that
hydrophobic property is uniquely assigned to highly hydrophobic
nature of PVF-HFP binder (Fig. 5).
It is well considered that surface area and porosity are key para-
meters to be explored for the electrode materials in the CDI systems.
Thus, the surface area of pristine AC, treated AC, CNTs and AC-CNTs
composites are evaluated by the Brunauer–Emmett–Teller (BET)
method and presented in Fig. 6 (Figure inset: the pore distribution of
9mAC:1CNTs). The following remarks can be drawn. First, the isotherm
shape of pristine and treated AC is characterized by type I according to
the IUPAC classification, with most of the nitrogen uptake occurring at
P/Po < 0.1, which indicates the presence of microporous structure of
AC [16,18,31–33]. The treatment process insignificantly affects both
the specific surface area (the value increases slightly from 950 m2/g to
1003 m2/g, ca∼5%) and the pore size (from 1.62 nm to 1.63 nm) of
AC. Meanwhile, the isotherm curve of CNTs is typical III form with a
slight rise at P/Po < 0.8 and steep rise from P/Po > 0.9. Finally, mAC-
CNTs composites behavior as typical-II isotherm, relating to
L.T.N. Huynh, et al. Synthetic Metals 265 (2020) 116415

Fig. 3. SEM images of composites with different mAC:CNTs ratios: a) 9:1 ; b)

8:2; c) 7:3.

mesoporous structure [10,25,34,35]. As clearly shown from Table 1

that while free standing CNTs and AC have much lower values in sur-
face area and pore size accordingly (110 m2/g for CNTs, 1.62 nm for
AC), all composite samples have bigger specific surface area (more than
400 m2/g) and larger pore size (in the range of 2.5-3 nm). On the one
hand, CNTs lead to reduced surface area of AC-CNTs composite when
partially blocking the micropore AC, on the other hand, the larger pore
size of CNTs composite certainly favors ion penetration and transpor-
tation during the charge-discharge CDI process, making Na+ (ionic
radius of 0.102 nm) and Cl- (ionic radius of 0.181 nm) easily trans-
portable during CDI adsorption and desorption.
To summarize, it can be concluded in this section that SEM/TEM/ Fig. 4. TEM images of composites with different mAC:CNTs ratios: a) 9:1 ; b)
IR/XRD and BET data support successful surface functionalization of 8:2; c) 7:3.
CNTs, AC materials that in its turn, would enhance interfacial com-
patibility between CNTs and AC and improve overall electrochemical parameter control throughout the whole production is very important
CDI performance while controlling initial characteristics of starting and is required to ensure high reproducibility of CDI materials pro-
CNTs and AC materials. It should be noted that such a precise duction at large scale.

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L.T.N. Huynh, et al. Synthetic Metals 265 (2020) 116415

Table 1
Specific surface area and pore size of samples
Specific Surface Area (m2/g) Average pore size (nm)

AC 1003 1.62
mAC 950 1.63
CNTs 110 2.90
9mAC:1CNTs 630 2.63
8mAC:2CNTs 528 2.78
7mAC:3CNTs 459 2.95

Fig. 7. Cyclic voltammograms of mAC:CNTs electrodes in 200 ppm NaCl so-

lution at scan rate of 20 mV/s.

Table 2
Specific capacitance and ohmic resistance of mAC-CNTs electrode
Electrodes Specific Capacitance (F/g) Ohmic resistance (Ω)

AC 30.1 15.5
9mAC:1CNTs 90.2 9.1
8mAC:2CNTs 69.5 10.8
7mAC:3CNTs 67.1 13.4
Fig. 5. Contact angle of 9mAC:1CNTs composite.

seen from Tables 1 and 2. Next, with increasing CNTs content in

Fig. 6. Nitrogen adsorption/desorption isotherm curves of pristine AC, mAC,
CNTs, and mAC-CNTs composites (Inset: DJH desorption pore distribution of
9mAC:1CNTs).
3.2. Electrochemical performance
In this section, CV, EIS and charge-discharge test are exploited for
understanding electrochemical properties of the electrode composites.
First, the inherent characteristic CV shape with the absence of redox
peaks, obtained from cyclic voltammograms is most closely associated
with the occurrence of a non- faradaic (i.e. capacitive) process, dealing
with the double layer formation and adsorption of ions present in the
solution at the surface of charged electrode (Fig. 7). Indeed, it was well
recognized in the literature that the ions were migrated on the mAC-
CNTs surface by electrostatic interaction to form the electric double
layer (EDL), the pore could act as electrochemically active sites and the
specific capacitance (Csp) is formed as a result of the double-layer ca-
pacitance [5,16,36,37]. Further, since the specific capacitance can be
calculated by integrating voltammogram area, the CV curve can be
equally expressed as specific capacitance vs potential. Certainly, a
larger specific surface area facilitates the formation of EDL, as clearly
composites, the specific capacitance of the electrode rises to a peak
value (at 10% of CNTs, i.e. for 9mAC:1CNTs) and then falls gradually.
Together with the above SEM/TEM characterizations it is understood
that an optimal content of CNTs, providing the most channels assessible
for ion transport (to maximize the charge), is attributed to an increase
of the specific capacitance. Beyond this content (> 10%), an excessive
amount of CNTs may lead themselves to self-agglomerated forms that
might impede the ion mass transport and make the capacitance dropped
again [2,20,38].
The potential of zero charge (the electrode potential at which in-
terface displays a net zero charge, EPZC) of 9mAC:1CNTs composite
electrodes can be estimated using cyclic voltammetry. As can be clearly
seen from the marked rectangle in the voltammogram of Fig. 7, EPZC
was calculated as +0.22 V vs. Ag/AgCl by averaging the location of the
‘V-shape’ at the forward (+0.28 V) and backward scans (+0.16 V). The
explicit shift of EPZC (from zero) towards a positive potential (+0.22 V)
is unambiguously linked to more negative surface charge (COO-, OH-)
accumulation, formed as a result of the surface functionalization of AC
and CNTs by HNO3 treatment (obviously EPZC of non-treated AC-CNTs
electrode is equal to zero when no surface functionalization (no charge
accumulation) occurs). This phenomenon was thoroughly studied and
well documented in the earlier papers of X. Gao et al. [39–41].
It is interesting to follow charge transfer resistance and capacitance
behaviors of composite electrodes when comparing both Nyquist Bode
representations of EIS data.
Evidently, Nyquist plots are consistent with CV data, presenting
behavior of a double-layer capacitor, with internal resistance (the
ohmic resistance of the active material including the electrolyte re-
sistance and connection resistance between the electrode and electro-
lyte) at high frequencies and charging resistance (Warburg region) at
low frequencies (Fig. 8). The variation in ohmic resistance is summar-
ized in Table 2.
In addition to Nyquist plots, Bode plots (Fig. 9a) also consider that
mAC-CNTs electrodes have lower charging resistance, attributed to a
better transport of electrolyte in composite to rapidly form mesopore
double layer. The variation of the capacitance as a function of AC

5
L.T.N. Huynh, et al.
Fig. 8. Nyquist plots of mAC:CNTs electrodes.
Fig. 9. (a) Bode plots of mAC:CNTs electrodes. (b) Capacitance versus fre-
quency of mAC:CNTs electrodes.
frequency is also presented in Fig. 9b. In summary, the comparative
study from Figs. 3, 4 and Figs. 7–9 and Table 2 prompts us to determine
a relationship between the large value of capacitance and favorable
charge transfer pathways and afterwards with the improved con-
ductivity in mAC-CNTs composite electrodes [14,20,38,42].
Regarding CDI recycle electrosorption performance, immediate
changes in the current strength are recorded when a constant potential
is applied to the electrode over a defined process time. Simultaneously,
the enforced changes in the electrode surface charge provoke a re-
arrangement of the ions in solution. As seen from Fig. 11a, a rapid in-
crease in the current occurred due to the migration of the NaCl ions
from the solution to the carbon surface is observed. Then, relatively
6
Synthetic Metals 265 (2020) 116415
Fig. 10. (a) Recycle electrosorption performance for 9mAC:1CNTs electrodes.
(b) The variation of desalination capacity during 100 cycles for 9mAC:1CNTs
electrode.
rapid decay of current occurs until the double layer is completely
formed. Importantly, the 9mAC:1CNTs electrode shows good cyclic
stability with 100% of capacitance is retained over 10 consecutive
potentiostatic cycles at 1.0/0 V (Fig. 10a). The variation of the average
SAC in every 10 cycles of 9mAC:1CNTs in long-cycle life (100 cycles)
performance were plotted and presented with the standard errors in
Fig. 10b. It can be seen from this figure that SAC retention ratio of the
CDI electrode, as high as 95.7% (13.5 mg/g vs 14.1 mg/g), reached
after 100 adsorption–desorption cycles at 1.0/0 V has indicated a good
cyclic stability of the above electrode composites.
Desalination experiments for 9mAC:1CNTs composites at two con-
centrations of 200 ppm and 1000 ppm NaCl are shown in Fig. 11. The
results show that the NaCl salt adsorption on the electrode is quite
good, with low salt (200 ppm) concentration, low current density value
is recorded and vice versa. The adsorption equilibrium is reached gra-
dually when most ions are absorbed electrochemically over the period
of ca. 10 min. As for 1000 ppm, this process is almost complete after
such a short period of 100-200 s. This difference is explained by the fact
that at a lower concentration, the ionic mobility is less, the ionic dif-
fusion path is more; thus, the ions are much slower adsorbed on the
surface of the electrode under the applied potential (longer adsorption
equilibrium is recorded) [35,43].
The SAC (mg/g), related to the number of ions adsorbed on the
electrode surface is calculated from the CDI performance. As shown in
Table 3, the electrosorption capacities of 9mAC:1CNTs, 8mAC:1CNTs
and 7mAC:3CNTs electrodes were 14.1 mg/g, 11.7 mg/g and 8.1 mg/g,
L.T.N. Huynh, et al. Synthetic Metals 265 (2020) 116415

Fig. 11. Real-time plot of conductivity versus time of 9mAC:1CNTs electrode in 1000 ppm and 200 ppm NaCl solutions at 1 V.

Table 3
Comparison of electrosorption capacity of various carbon-based composite
electrodes
Electrode Voltage (V) Salt adsorption capacity
(mg/g)

CNT/ACF[46] 1.2 6.4

Carbide-Derived Carbon[33] 1.4 15.2
Graphene-coated Hollow Mesoporous 1.6 2.3
Carbon Sphere[47]
AC granule[48] 1.5 14.6
CNTs-RGO-10[49] 1.2 1.4
CNT/graphene[50] 2.0 26.4
AC@CNTs[38] 1.5 15.6
Date seeds biomass-derived activated 1.2 22.5
carbon[51]
Mn3O4 nanowires/rGO[52] 1.2 34.5
α-MnO2/f-AC (Palm Tree derived AC) 1.2 17.8
[53]
Graphene/CNTs/ZnO NPs[54] 1.2 28.62 Fig. 12. CDI Ragone plot of mAC:CNTs electrodes in 1000 ppm NaCl at 1 V.
9mAC:1CNTs – this work 1.0 14.1
8mAC:2CNTs – this work 1.0 11.7
materials in terms of the desalination performance [52,54,56].
7mAC:3CNTs – this work 1.0 8.1
The specific energy consumption (SEC) of CDI cell can be de-
termined by using the equations (4) below [57–59]:
respectively. It should also be noted that at as low as 1.0 V applied
Ae tcharge
voltage in our study, the obtained values of SAC are comparable to SEC =
qtcharge
∫0 iE dt
(4)
those of current AC-based CDI electrode materials (10-15 mg/g in
average), but are inferior to those of hybrid materials containing both
redox metal oxides and other allotropes of carbon (CNTs, Graphene, Where, i is current during the electro-adsorption process, Ae is electrode
AC) (in hybrid capacitive deionization (HCDI) or Battery Electrode area, q is the flowrate and tcharge is the duration of the electro-adsorp-
Deionization (BDI) configurations) [44,45]. tion process. The SEC value of 0.312 kW h/m3 was calculated using (4)
CDI Ragone plot, combining two important parameters (SAC vs. for 9mAC:1CNTs electrode (with a feed solution of 1000 ppm NaCl).
ASAR), is usually plotted to evaluate the overall desalination perfor- Obviously, the energy consumption of the auxiliary components such as
mance of the CDI electrode [55]. As shown in Fig. 12, being displayed the process control system, current converters, valves, and pumps
in the upper and right region of Ragone plot, 9mAC:1CNTs possesses should additionally be taken into account. Nevertheless, it is worth
the highest SAC and fastest ASAR. The performance of 9mAC:1CNTs considering the energy efficiency of CDI technology (0.1–0.59 kW h/
electrode can be understood when much larger surface area, higher m3) for brackish (low feed salinity) water, where the performance of
conductivity and more accessible channels for ion transport were pro- CDI could be much more comparable to RO (2.25 kW h/m3) or ED (2.03
vided in the latter. In this regard, Ragone plot is quite useful when kW h/m3) [4].
representing the comprehensive comparison of different electrode

7
L.T.N. Huynh, et al.
4. Conclusion
Physicochemical and electrochemical properties of the fabricated
mAC-CNTs composites were thoroughly characterized. From a struc-
tural viewpoint, it is found that 9 mAC:1CNTs composites are best
optimized as compared with free standing mAC, CNTs as well as dif-
ferent mass ratio mAC:CNTs composites. From an electrochemical
viewpoint, CV, EIS, charge/discharge test, Ragone plot confirm ex-
cellent properties of the composites in term of CDI electrodes. Overall,
incorporating CNTs into coconut shell-derived mAC could form an in-
novative, effective and very promising electrode material for in-
expensive, controllable and large scale CDI production in developing
countries. Along with electrode material compositional optimization,
the work is underway to address the optimum design and assembly of
energy-efficient, high salt removal capacity of custom-built CDI sys-
tems.
Author statement
-This manuscript has not been published and is not under con-
sideration for publication elsewhere. We have no conflicts of interest to
disclose.
-We confirm that the manuscript has been read and approved by all
authors. We also confirm that the order of authorship has been agreed
upon, and the criteria for authorship as defined in the “Uniform re-
quirements for manuscripts” have been met.
-We wish to confirm that there are no known conflicts of interest
associated with this publication, and there has been no significant fi-
nancial support for this work that could have influenced its outcome.
-We confirm that we have given due to consideration to the pro-
tection of intellectual property associate with this work and that there
are no impediments to publication, including the timing of publication,
for intellectual property. In so doing, we confirm that we have followed
the regulations of our institution concerning intellectual property.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
Materials design and CDI electrochemical performance are funded
partly by Basic research program of National Foundation for Science
and Technology Development (NAFOSTED), 104.03-2018.344. CDI
prototype design and operational parameter testing are supported by
Applied Program on Science and Technology (KC.02.24/16-20). Minor
financial resources for short visit/internship from Czech -Vietnam
Academy cooperation (QTCZ. 01.02/20-21, Thi Thu Vu), Japan Student
Services Organization (JASSO) exchange program (Thi Thom Nguyen
and Thi Kieu Anh Vo) are also acknowledged.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.synthmet.2020.
116415.
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