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We systematically summarized current progress on graphene-based materials for capacitive

deionization.
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Graphene-based materials for capacitive deionization

Received 00th January 20xx,
Accepted 00th January 20xx Peiying Liua, Tingting Yana, Liyi Shia, Ho Seok Park,b Xuecheng Chenc, Zhigang Zhaod and
DOI: 10.1039/x0xx00000x Dengsong Zhanga,*
www.rsc.org/ Capacitive deionization is an emerging technology for energy-efficient water desalination, and
attracts more and more attention in recent years. The capacitive deionization technology is based on
ion electrosorption at the surface of a pair of electrically charged electrodes, which is commonly
composed of carbon materials. Among numerous electrode materials, graphene-based materials are
outstanding, playing a vital role during the deionization process due to their intriguing features. After
a brief introduction of the theory and instruments of capacitive deionization, we systematically
summarize current progress on graphene nanosheets, porous graphene, graphene-based composites,
surface tuned graphene and its composites as electrodes for capacitive deionization. We also present
our perspectives on the development of graphene-based electrodes for capacitive deionization.
method based on electric double-layer capacitors (EDLCs).14

1. Introduction The charged ions can be adsorbed onto the surface or into the
pores of the porous electrodes to form EDLCs when the
Water scarcity has become one of the most serious global
external voltage is applied, and released from the electrodes
challenges due to the increasing population, the industrial
when the charge is removed or reversed.15, 16 According to the
development, and the contamination of freshwater resources.1,
2 CDI process, the electrode material is crucial to the
To tackle this threatening issue, novel technologies for
performance of CDI.17 The ideal electrode for CDI should
purifying water from sea or brackish water are urgently
possess high specific surface area with a pore structure
required.3, 4 The desalination of seawater or brackish water is
offering high ion mobility, high conductivity, good wettability,
an effective method to solve this crisis issue.5, 6 Over the years,
and be made of a low-cost, scalable, and easily processable
a multitude of desalination methods have been developed
material.18 Carbon materials meet most of these criteria and
among which distillation,7 reverse osmosis,8, 9 and
the development of CDI electrodes has been mostly focused
electrodialysis10 are the most commonly known and
on carbon materials like carbon aerogel,19-23 activated
widespread technologies. However, the limitations of these
carbon,24, 25 ordered mesoporous carbon,26-32 carbon
traditional methods, such as high cost, excessive energy
nanotubes,33-37 activated carbon fiber38-41 and their
consumption, poor efficiency and being less environment-
composites.42-47 However, the development has been limited
friendly are quite visible.11, 12 Therefore, the search for an
by these porous carbon materials with too much microspores
economical, efficient and environment friendly method for
or low electrical conductivity. Therefore, it is urgently desired
desalination is urgently needed.
to find a new material with superior physical and chemical
Capacitive deionization (CDI), which is environmentally
properties for CDI.
friendly, energy efficient and cost effective for water
The latest material to capture the attention of researchers is
purification in comparison with other conventional approaches,
graphene, a two-dimensional layer of carbon atoms arranged
has drawn much attention from the researchers worldwide in
in a hexagonal crystalline structure, 48-54 which has prospects in
recent years.13 Typically, the CDI performance of the
a wide range of important domains, such as energy,55-58
concerned carbon materials was evaluated in a recycle system,
electronics,59-61 photonics and sensing.62-64 The interest in
as shown in Fig. 1. The CDI is an electrochemically controlled
graphene originates from its unique physicochemical
properties, notably the exceptionally high surface area,
aResearch Center of Nano Science and Technology, Shanghai University, Shanghai electron and thermal mobility, and mechanical strength.65-67
200444, China. E-mail: dszhang@shu.edu.cn; Fax: +86 21 66136079 These exceptional properties have triggered extensive efforts
b School of Chemical Engineering, Sungkyunkwan University (SKKU), Suwon 440-
746, Republic of Korea to apply graphene into all fields of technology, from electronic
cInstitute of Chemical and Environment Engineering, West Pomeranian University
systems to biomedical devices.68-77 Also, graphene is one of the
of Technology, ul. Pulaskiego 10, 70-322, Szczecin, Poland most promising CDI electrode materials with good salt removal
d Key Lab of Nanodevices and Applications, Suzhou Institute of Nano-Tech and
Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123, P. R. China ability due to its high theoretical specific surface area, good
This journal is The Royal Society of Chemistry 20xxJ. Name., 2013, 00, 1-3 | 1
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Fig. 1 Schematic illustration of the CDI set-up
electrical conductivity and controllable morphology current (Fig. 2).96 This theory considered both the flow
structure.78-82 Over the past few years, considerable efforts direction of the aqueous solution through the spacer channel,
(~75 papers) have been dedicated to the design of graphene- and the movement of salt in and out of the electrodes. The
based materials for CDI.83, 84 There are several reviews for the theory of CDI is relatively mature. However, with the fast
various carbon-based electrodes including graphene-based development of CDI, the current CDI models expect the further
electrode previously, but none of systematically summarized modification to adapt the practical applications.
current progress for graphene-based electrodes for CDI has In the progress of CDI technique, CDI instruments play a play
been published.17, 83, 85-92 Therefore, the graphene-based an important role in the desalination performance. Recently, a
materials for CDI are the focus of this review. This review will variety of novel instruments with unique features and novel
lay a solid scientific foundation for the design and application functionalities for CDI have been designed. There are mainly
of graphene-based electrodes. two kinds of CDI instruments, one is symmetric CDI and the
In this work, we will review the recent research activities in other is asymmetric CDI. The first and widely-utilized CDI
graphene-based materials for CDI and lay emphasis on the instrument is flow-through CDI (Fig. 3A).97 In 1960, Blair et al.
preparation methods for graphene-based materials and their pioneered the work of the flow-through CDI.98 Afterwards,
desalination performance. We also discuss the impacts of the Oren and Soffer studied the electrochemical parametric
specific surface area, porous structure, hydrophilic, and pumping by utilizing flow-through CDI in the 1970s and
electrical conductivity of graphene on the desalination 1980s.99, 100 This instrument was subsequently utilized in a
performance. These recent advances in materials preparation wide variety of works. 101, 102, 103 In the 1970, Johnson et al.
and configuration design will bring new insights into the future developed a osmosis CDI instrument, in which the feed flow
of graphene-based electrodes. Finally, we will highlight the
main challenges to overcome in order to realize the full
potential of graphene-based materials in CDI application.
2. The theory and instruments of CDI

The CDI technique is based on the theory of EDLs. The initial
CDI models for EDL structure models are Helmholtz EDL
model93 and GouyChapmanStern (GCS) EDL model.94 An
advance in the equilibrium EDL structure model named
modified Donnan (mD) model can account for the confined
Fig. 2 Schematic view of the time-dependent two-dimensional porous electrode
nature of the micropores in CDI electrodes. ).95 In the mD
model, combining a sequence of sub-cells in the flow direction, with ion fluxes
model, the micropores are considered to have strongly into the electrode. A symmetric CDI geometry is assumed, thus only half of a cell
overlapped double layer and so the classical Donnan is depicted. The electrode contains an electrolyte-filled volume allowing for ion
assumption of a uniform pore electrostatic potential can be transport, and carbon material in which ions and charge are stored. Electrical
utilized. Recently, Porada et al. put forward 2D porous current (denoted by +) flows through the conductive carbon material.
electrode theory to describe the electrosorption and electrical Copyright 2013, the Royal Society of Chemistry.
2 | J. Name., 2012, 00, 1-3 This journal is The Royal Society of Chemistry 20xx

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directly osmosis the electrodes (Fig. 3B).104 Avraham et al. View Article Online
utilized the osmosis CDI instrument to study the fundamental DOI: 10.1039/C7TA02653F
performance parameters.105 They noted that the osmosis CDI
allowed for faster cell charging than flow-through CDI.106 In
2012, the desalination battery was proposed, which utilize two

battery electrodes for desalination (Fig. 3C). This instrument is
promising for high salinity water desalination and allows high
salt sorption. However, the desalination battery is instability
due to the Faradaic reactions. In 2014, a new CDI instrument
came out which leveraged carbon flow electrodes, or carbon
slurry electrodes (Fig. 3D).107 This flow-electrode CDI can
potentially enable compact and low resistance systems. In
addition, Porada et al. introduced another form of electrodes
in motion by using the moving wires to perform
desalination.108 Hatzell et al. developed a new type of

suspension-electrode CDI for desalting brackish and seawater
by using carbon suspensions (Fig. 3E).109
Recently, asymmetric CDI attracts great interest. In 2006,
Lee et al. proposed membrane CDI (MCDI) (Fig. 3F).93 In the
flow-through MCDI, a free-standing cation exchange
membrane is placed before the cathode, and a free-standing
anion exchange membrane is placed before the anode. After
adding membranes, the charge efficiency can be effectively
improved due to the membranes block co-ions from carrying
parasitic current.110 Alternatively, it is possible to directly
grafting ion-selective groups onto porous carbon (Fig. 3G),
which can reduce the internal resistance and production
cost.111, 112 In the ion-selective flow-through CDI, the functional
groups can minimize the co-ion expulsion effect and increase
the charge efficiency. Recently, Gao et al. developed an Fig. 3 (A)-(E) Symmetric CDI, including (A) flow-through CDI, (B) osmosis CDI, (C)
inverted CDI by using an anode with net negative surface desalination battery (D) flow-electrode CDI and (E) suspension-electrode CDI.
(F)(K) Asymmetric CDI, including (F) flow-through MCDI, (G) ion-selective flow-
charges and a cathode with net positive surface charges (Fig.
through CDI, (H) hybrid CDI, (I) inverted CDI, (J) flow-electrode CDI and (K)
3H).113 The salt separation in this system is achieved in an
Asymmetric flow-electrode CDI.
opposing manner to the conventional CDI system, when the
system is charged using a power source, cations and anions are
desorbed at the anode and cathode, respectively. Inspired by vast improvements in desalination performance. Therefore,
the previously developed desalination battery, Lee et al. the asymmetric CDI is an important future research direction.
reported a novel desalination technique referred to as hybrid
CDI (Fig. 3I).114 The hybrid CDI exhibited more than double the
ion removal sorption capacity than a typical CDI system. Jeon 3. Types of graphene-based materials for CDI
et al. designed and experimentally tested a novel membrane
CDI process for seawater desalination (Fig. 3J).115 It is 3.1 Graphene for CDI
demonstrated that a flowing suspension carbon can be applied Graphene is a promising material for the development of high
to the desalination of high salinity streams. However, in performance CDI electrodes due to its extraordinary
practical cases, the operation voltage of flow-electrode CDI is conductivity, tunable surface properties and morphology,
usually limited by the decomposition potential of water, which outstanding physical and chemical properties.117-119 Graphene
is not beneficial for the desalinization performance. Thus, Xu is composed of pure carbon in a single layer two-dimensional
et al. proposed a novel asymmetric flow-electrode CDI device (2D) structure that provides a very large specific surface
by using an activated carbon (AC)/MnO2 suspension as the area,120, 121 which is beneficial to the ions storage on the
positive electrode and AC suspension as the negative electrode surface. In theory, the parallel plates could provide extensive
(Fig. 3K).116 In the asymmetric flow-electrode CDI, the channels through which salt ions can easily access the surface
operation voltage can be improved to be 1.8 V, and a high salt of each graphene sheet with low diffusion resistance.122, 123
removal efficiency is much higher than that for conventional The high electrical conductivity of graphene sheets could
flow-electrode CDI. eliminate the need for conductive additives, enabling
As discussed above, the asymmetric CDI is promising for the graphene-based electrodes with increased specific
practical applications. Because the asymmetric CDI can capacitance.124-126 Furthermore, the 2D layer structure endows
minimize the co-ion effects and achieve high adsorption the graphene electrodes with good mechanical flexibility,
capacity and high charge efficiency. The asymmetric flow- which makes the graphene sheets easy to assemble into
electrode CDI is still in its infancy, and there is the potential for graphite paper with robust mechanical stability.127, 128

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Therefore, these intriguing features make graphene an carbon electrode highly charged multivalent ionsView with smaller
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attractive electrode material for CDI application. hydrated radius would be strongly attracted. The results
DOI: 10.1039/C7TA02653F
3.1.1 Graphene nanosheets for CDI. With the increasing of confirmed that the, graphene would be a good candidate as
chemical approaches for the large-scale production of highly electrodes material area (2600 m2 g-1) and high conductivity of
conducting graphene sheets, the application of graphene is graphene (7200 S m-1).

becoming more widespread.129-137 Since Stoller et al. Analogously, Li et al. synthesized the graphene-like
successfully applied graphene as an electrode material in nanoflakes by a modified Hummers method using hydrazine
ultracapacitors with a high specific capacitance of 135 and 99 F for reduction.102 It was found that the ratio of nitric acid and
g-1 in aqueous and organic electrolytes, respectively.138 Such a sulfuric acid plays a vital role in determining the specific
good capacitive performance of graphene also enables itself to surface area of graphene-like nanoflakes (Fig. 5A). The specific
be a promising electrode material in CDI. In 2009, Li and co- surface area of graphene-like nanoflakes is 222.01 m2 g-1. Fig.
workers pioneered the application of graphene as an 5B illustrates the principle of CDI and the mechanism of how
electrosorptive electrode of CDI.139 The graphene was ions are electrosorbed onto activated carbon and graphene-
fabricated by a modified Hummers method and a hydrazine like nanoflakes, respectively. The graphene-like nanoflakes has
reduction process. The initial attempt to use graphene for CDI an interlayer structure that is more accessible for ions, while
resulted in relatively low Na+ electrosorption capacity (1.85 mg activated carbon has a large fraction of inaccessible small
g-1), due to the tendency of graphene to aggregate, which micropores (Fig. 5C, D and E). The salt adsorption capacity of
resulted from relatively low surface area (14.2 m2 g-1). They the graphene-like nanoflakes was 1.35 mg g-1 for Na+ in a NaCl
demonstrated that the electrosorption of NaCl onto graphene solution with an initial conductivity of 55 S cm-1 at 1.2 V,
electrodes is driven by a physisorption process by taking into which was higher than that of activated carbon under the
account the thermodynamic parameters. same experimental condition. Actually, the micropores in
When the graphene nanoflakes synthesized by the modified activated carbon can increase the surface area and offer more
Hummers method were employed for the electrosorption of adsorption sites. But some dead pores and the lack of
ferric chloride140, it was found that the optimum flow rate and interconnected network have unfavorable influence on the salt
electrical voltage were at 25 mL min-1 and 2.0 V, and the adsorption capacity and rate. In addition, the CDI performance
electrosorption capacities of the cations followed the order of is not only related to the surface area but also to the pore
Fe3+ > Ca2+ > Mg2+ > Na+. It means that when the hydrated structure, conductivity and wettability of the electrode
cations are electrically adsorbed on a negatively charged materials. Although the surface area of activated
Fig. 4 Summary of graphene-based materials for CDI. (A) Graphene nanosheets, (B) Porous graphene, (C) Graphene-porous carbon composites, (D) Graphene-carbon nanotube
composites, (E) Graphene-activated carbon nanofibers composites, (F) Graphene-metal oxide composites, (G) Graphene-polymer composites, (H) Multi-component graphene-
based composites, (I) Nitrogen-doped graphene, (G) Nitrogen-doped Graphene based composites, (K) Functionalized graphene, (L) Functionalized graphene based composites

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carbon is much higher than graphene, many micropores in graphene with a high deoxidization and exfoliation degree. In
activated carbon is disordered, which increase the transport order to prepare high-quality graphene with a low presence of
resistance of salt ions through the pore network. As a result, oxygen-containing groups, our group reported a pyridine-
the surface area of activated carbon has not been utilized fully, thermal strategy for successive exfoliation and reduction of
leading to smaller specific capacitance than graphene. In graphite oxide by using pyridine as the intercalating agent and
addition, the conductivity of activated carbon is lower than dispersant (Fig. 6).154 As an intercalating agent, the pyridine
graphene, which also increase the diffusion resistance of the molecules can intercalate into graphite oxide basal planes
salt ions. In comparison to activated carbon, graphene shows a through the - accumulation between the phenyl ring of
promising potential for applications in brackish water pyridine and the aromatic system of graphite oxide, which is
desalination and drinking water purification. favorable to inhibit the re-stacking of graphene during the
Unfortunately, the most common reducing agents used to reaction process. In addition, as a dispersant, pyridine can
produce graphene, such as hydrate hydrazine,141 improve the dispersity of graphene. The obtained graphene
142, NaBH 143 and alkali,144 are almost always
hydroquinone 4 shows a loosely layered structure and the gap between the
highly toxic and even explosive. Therefore, many attempts sheets is obvious due to the effective exfoliation. The CDI
have been made to develop green reductants including performance of the as-prepared graphene was also
urea,145 metal powders,146, 147 sugar,148 vitamin C,149 150 and investigated. After 120 min, the conductivity of the NaCl
alcohol.151 Although great achievements have been made, the aqueous solution reduced from 86.9 to 10.2 S cm-1, and the
reduction efficiency and exfoliation degree may be salt adsorption capacity is calculated to be 0.88 mg g-1. The
compromised, and also the reducing process is complicated.152, cross-linking and porous structure is formed through the loose
153 Hence, a more feasible and environmentally friendly stacking between the graphene sheets, which provides a
chemical reduction approach is urgently desired to produce pathway for the salt ions to be transported easily during the
CDI process.
Interestingly, there is another highly facile and rapid method
for the preparation of scalable large-area graphene using
chemical free and energy efficient technique for the reduction
of chemically synthesized graphite oxide paper by focused
solar irradiation method.155 The as prepared graphene has high
specific surface area (273.2 m2 g-1). And high value of
electrosorption capacity of 9.6 mg g-1 was obtained in 584.4
mg L-1 NaCl solution in 60 minutes. This indicates huge
potential applicability of the graphene as electrode materials
for CDI.
From the above, the salt adsorption capacity of graphene
nanosheets is not satisfactory for lack of pores in the graphene
nanosheets. Still, graphene nanosheets, despite a lower
surface area than activated carbon electrodes, demonstrated
higher electrosorption capacity due to the interlayer structure
of graphene that is more accessible to ions than the small
micropores of activated carbon. These results highlighted the
potential of graphene for CDI applications, with the condition
that the surface area of the graphene-based electrode can be
increased. In addition, a multitude of novel method to prepare
high-quality graphene accelerates the graphene-based
electrodes in the CDI application.
2.1.2 Porous graphene for CDI As mentioned above,
Fig. 5 (A) Comparison of electrosorptive performance by employing graphene-like graphene shows great potential in the CDI application, but the
nanoflakes and activated carbon at the same experimental condition, the pictures at
salt adsorption capacity of the graphene nanosheets is still far
top-left and top-right depict the pore size distribution of activated carbon and
graphene-like nanoflakes below 10 nm, respectively. (B) Mechanism of CDI employing
from expectation. This can be attributed to the irreversible
activated carbon and graphene-like nanoflakes electrode. TEM observation images of aggregation and restacking of graphene owing to the strong -
activated carbon. (C) and graphene-like nanoflakes in low (D) and high (E) magnification, interactions and van der Waals forces between the planar
respectively. Copyright 2010, American Chemical Society. basal planes of graphene sheets,156, 157 which results in a

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Fig. 6 Procedure for the preparation of graphene by the pyridinethermal strategy. Copyright 2012, the Royal Society of Chemistry.
decrease in the desalination performance. Therefore, a surface area of 3D macroporous graphene is 339 m2 g-1. 3D
number of strategies have been developed to prevent macroporous graphene was firstly used as a CDI electrode with
aggregation of graphene sheets in order to increase effective good electrosorption capacity. When the voltage increased
specific surface area and promote transport of ions.158-160 from 1.2 V to 2.0 V, the electrosorptive capacity of the 3D
Generally, the desalination performance is significantly macroporous graphene electrodes increased from 1.97 mg g-1
affected by the ion accumulation and transport, which usually to 5.39 mg g-1. However, the increment of electrosorptive
depend on the microstructure and specific surface area of the capacity of graphene electrodes is not notable, only from 1.27
electrode materials. These can be improved by fabricating mg g-1 to 2.68 mg g-1 in a NaCl aqueous solution with an initial
interconnected electrode materials with a high specific surface conductivity of 105 S cm-1 with the applied voltage of 1.6 V
area and porous structure.161-164 To address these issues, (Fig. 7C). When the voltage increased from 1.2 V to 2.0 V, the
graphene-based macrostructures with 3D porous networks,165- electrosorptive capacity of the 3D macroporous graphene
169 such as aerogels,170-172 hydrogel,173-176 foams,177-181 electrodes increased from 1.97 mg g-1 to 5.39 mg g-1 (Fig. 7D).
frameworks,125, 182 and sponges,183-185 have recently attracted Considering the pore structure, effective specific surface area
considerable interest. These 3D graphene materials, consisting and the electrical conductivity, it is believed that the 3D
of micro-, meso- and even macroporous networks, can provide macroporous graphene with a high specific surface area and
high surface area, fast ion/electron transport. Several groups 3D porous conductive network is a good candidate electrode
have confirmed that the formation of 3D macroscopic material for CDI application.
structures of graphene can prevent inter-sheet restacking.186- Alternatively, 3D graphene sponge is another structure to
190 In addition, it was reported that the 3D macroscopic prevent the aggregation of graphene sheets, and enlarge the
interpenetrating architectures of electrode materials were specific surface area, thus improve the electrosorption
beneficial for the transport of ions and electrons in the capacity. Yang et al reported on the sponge (polyurethane)-
electrode; thereby higher salt adsorption capacity was templated strategy to prepare sponge-like graphene with high
obtained.191-194 specific surface area (305 m2 g-1) and favorable pore size
In order to prevent the aggregation and restacking of distribution as CDI electrode materials (Fig. 8A).191 As shown in
graphene sheets, our group designed the 3D macroporous Fig. 8B, C and D, the sponge-like graphene exhibits
graphene architectures by a simple template-directed method macroporous structure with well-defined interconnected
using polystyrene microspheres as sacrificial templates (Fig. pores at a size range from 76 m to 379 m. The capacitive
7A).195 The TEM image in Fig. 7B confirmed that the deionization behavior of sponge-like graphene and graphene
macroporous network of 3D macroporous graphene with electrodes were carried out in a 20 mL NaCl aqueous
intact continuous walls does not collapse, and the specific

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Fig. 7 (A) Schematic illustration of the 3D macroporous graphene for CDI application. (B) TEM images of 3D macroporous graphene. (C) CDI profiles of the 3D macroporous
graphene and traditional graphene electrodes under 1.6 V. (D) The electrosorption capacity comparison of 3D macroporous graphene and traditional graphene electrodes under
various voltages. Copyright 2013, the Royal Society of Chemistry.
solution with an initial conductivity of 106 S cm-1 and flow 3D porous graphene for practical applications.
rate of 3 mL min-1 at 1.5 V. The resulting macroporous In order to enlarge the effective specific surface area and
materials composed of graphene nanosheets exhibited the CDI improve the CDI performance, some recent reports proposed
performance with a superior electrosorptive capacity of 4.95 in situ defect etching methods to enlarge the specific surface
mg g-1 and a fast desorption rate. The sponge-like strategy area of graphene, including using H2O2,192, 197 KOH,198 KMnO4
199as etching agent to produce holey structured graphene.
offers a facile and variable route to rationally design and
prepare macroporous structured graphene-based electrode Hierarchical structures could offer a huge increase in specific
materials for CDI. surface area due to the large range of pores, having great
Similarly, Pan et al. fabricated a novel graphene sponge via potential in energy storage, energy conversion, drug delivery
directly freeze-drying graphene oxide solution followed by and catalytic applications.200-202 For example, Li and coworkers
annealing in nitrogen atmosphere.196 The obtained graphene presented a KOH-activated graphene by using KOH as the
sponge displays a porous structure with a high specific surface etching agent that has an ultrahigh specific surface area
area of 356 m2 g-1 with a pore volume of 1.51 cm3 g-1. The of3513 m2 g-1 and good electrical conductivity of 104 S m-1.198
graphene sponge electrode exhibits an electrosorption During the activation process, carbon can be etched by KOH,
capacity of 14.9 mg g-1 due to the unique 3D interconnected and the graphene forms a 3D network structure with a large
porous structure, large accessible surface area and low charge portion of micropores in graphene planes. The higher porosity
transfer resistance when the initial NaCl concentration is ~500 and high conductivity of the KOH-activated graphene, which
mg L-1 at 1.2 V. The graphene sponge electrode can be facilitates the ion transport. Consequently, a high
completely regenerated and reused for over 30 cycles without electrosorption capacity of 11.86 mg g-1 was achieved in a 74
any declination. The graphene sponge is promising to be used mg L-1 NaCl solution at 2.0 V. The high performance of KOH-
as electrode material for actual application of CDI. The 3D activated graphene makes it an ideal electrode material for CDI
graphene-based materials for CDI include 3D macroporous in miniaturized water-cooling system.
graphene and graphene sponge. Both of them possess However, when the external electrostatic field is relatively
abundant interconnected porous structures, which provide weak, the ion diffusion through micropores into the internal
lots of adsorption sites and can capture more salt ions. pores is hampered, thus decreasing the ion storage. In other
Therefore, 3D graphene-based materials with a porous words, the accessible surface area and space cannot be
structure can be applied in the CDI. It is also a big challenge to entirely utilized to accommodate ions.203 Thus, Pan group
develop a simple, green and cost-effective method to fabricate proposed a carbothermal strategy to prepare graphene sheets

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with unique mesoporous morphology by using KMnO4 as the porous graphene showed a high salt adsorptionView capacity of
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etching agent.204 Clearly, the mesoporous graphene displays a 14.7 mg g-1 in a 500 ppm NaCl aqueous solution at 1.2 V, and
DOI: 10.1039/C7TA02653F
large specific surface area of 474 m2 g-1 with a pore volume of exhibit higher salt adsorption rate than the 3D graphene
2.81 cm3 g-1, much higher than those of graphene (106 m2 g-1 electrodes. The 3D hierarchically porous graphene electrodes
and 0.23 cm3 g-1). The electrosorption experiments were also exhibited a better regeneration performance in the

performed in a NaCl solution with an initial concentration of repeated electrosorptiondesorption experiments. The unique
~500 mg L-1 at an applied voltage of 1.2 V. The electrosorption combination of the hierarchically porous structure and
capacity of mesoporous graphene is calculated to be 14.2 mg graphene building block may open opportunities to create a
g-1. The mesoporous graphene electrode can also be new class of high-performance materials suitable for CDI.
completely regenerated and reused for over 30 cycles without Alternatively, Kong et al. reported the construction of 3D holey
obvious declination. graphene hydrogel with in-plane pores by hydrothermal
It is generally acknowledged that hierarchically porous reduction of graphene oxide sheets (Fig. 8).192 During this
carbon combines the structural advantages of macropores and process, the reduced graphene oxide sheets self-assemble into
micro/mesopores. In the case of hierarchically porous carbon, interconnected holey graphene hydrogel, and the H2O2
macropores serving as ion-buffering reservoirs guarantee a preferentially etches the defective site on the reduced
shorter ion diffusion distance to the pores, and graphene oxide sheets to produce in-plane pores. The unique
micro/mesopores can provide efficient pathways and large architecture of the holey graphene hydrogel provides not only
accessible surface areas for ion transport and charge a large specific area (1261.7 m2g-1) for electrosorption of ions
storage.205, 206 Our group developed an approach that can form but also abundant in-plane pores, enabling efficient transport
ample micro-/mesopores across the highly interconnected 3D of ions. Moreover, the interconnected structure reduces
graphene sheets via the combination of in situ defect etching resistance against electron transport. As a result, the
and template-directed methods (Fig. 9).207 The as-obtained 3D electrosorption capacity of holey graphene hydrogel reaches a
graphene with hierarchically porous structure is composed of value as high as 16.0 mgg-1 when feeding a NaCl solution with
3D graphene architecture with ample micro-/mesopores an initial concentration of 500 mgL-1 at an applied voltage of
across the highly interconnected macroporous walls. The high 1.2 V. The holey graphene hydrogel is considered to be a
specific surface area (824 m2 g-1), hierarchically porous potential for CDI applications and beyond.
structure (micro-, meso- and macropores), high conductivity In addition, El-Deen et al. presented a novel and facile
and good wettability of 3D hierarchically porous graphene can strategy for fabrication of 3D activated porous graphene.208
ensure abundant adsorption sites and efficient electron and Briefly, thiocarbohydrazide coated silica nanoparticles
ion transport. In the CDI experiments, the 3D hierarchically
Fig. 8 (A) Schematic representation of the procedure for preparing sponge-like graphene. The down part gives the photo images of the sponge (B), sponge saturated with graphite
oxide solution (C), and sponge-like graphene (D). Copyright 2014, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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Fig. 10 Schematic illustration of the preparation of graphene hydrogels and the

process of CDI desalination. Copyright 2016, Tsinghua University Press and
Springer-Verlag Berlin Heidelberg.
areas (up to 778.5 m2 g-1).

In summary, graphene-based material as a promising
candidate has been widely used in the CDI application. Table 1
summarizes the salt adsorption capacity among various
Fig. 9 (A) Schematic illustration of the construction of 3D hierarchically porous
graphene architectures. Although the graphene nanosheets
graphene. Copyright 2016, the Royal Society of Chemistry.
showed a lower surface area, the desalination performance is
superior to activated carbon. Fortunately, the specific surface
intercalated graphene sheets are used as a sacrificial material
area of the graphene-based electrode can be increased by
for creating mesoporous graphene followed by alkaline
tuning the morphologies, structures and pores. Thus, many
activation process. This fabrication procedure meets the ideal
researchers have made great efforts to construct different 3D
desalination pore diameter with a high specific surface area
porous structures with various pores in order to achieve high
2680 m2 g-1 of activated 3D graphene-based micropores. The
specific surface area, which provide lots of adsorption sites
desalination performance of the fabricated electrodes was
and can capture more salt ions. It has been demonstrated that
evaluated by carrying out single pass mode experiment under
micro- and mesopores are essential for the CDI application,
various cell potentials with symmetric and asymmetric cells.
because micro- and mesopores can increase the surface area
The asymmetric charge coated microporous activated
and thus offer more adsorption sites. But some dead pores
graphene exhibits exceptional electrosorption capacity of
and the absence of interconnected network have unfavorable
18.43 mg g-1 at a flow rate of 20 mL min-1 upon applied cell
influence on the salt adsorption capacity and rate. Through the
potential of 1.4 V with an initial NaCl concentration of 300 mg
above researches, macropores in 3D graphene can guarantee a
L-1, high charge efficiency, good recyclability. This present
short diffusion distance. The results strongly demonstrated
strategy provides a new avenue for producing ultrapure water
that the 3D graphene-based materials have good desalination
via green capacitive deionization technology.
performance. However, the accessible surface area and ion
Gelation is another simple, effective, and straightforward
transport in the 3D macroporous graphene need to be
route to fabricate 3D porous macroscopic materials. Kim et al.
improved due to the lack of micro- and mesopores. Also, it has
presented an interfacial gelation process to fabricate large-
been demonstrated that hierarchical porous structures
scale 3D porous graphene hydrogel films with simple
(intertwined micro-, meso-, and macropores) are beneficial to
immersion of arbitrary Zn objects in aqueous dispersions of
ionic mass transportation. It is no doubt that the construction
graphite oxide.165 This gelation method enables a wide range
of a hierarchically porous architecture with an enormous
of controllable 3D gel structures as well as macroscopic objects
porosity as well as a perfect pore interconnection can enhance
based on any desired structure. The graphene sheets were
the salt adsorption capacity. It is also a big challenge to
interconnected in a quasi-parallel manner to form an open
develop a simple, green and cost-effective route to fabricate
porous morphology with a large range of pore sizes from tens
3D porous graphene architectures to further improve the salt
of nanometers to several micrometers. Interestingly, the
adsorption capacity.
introduction of various template structures at the Zn surface
2.2 Graphene-based composites for CDI
facilitates a straightforward route for fabricating 3D
macroscopic graphene gels with any arbitrary shape. The pristine graphene prepared by either chemical or thermal
Accordingly, the graphene hydrogel films exhibit high specific reduction of the graphene oxide always exhibits a relatively
low electrosorptive capacity due to the agglomeration of

Chemistry
graphene sheets and does not reflect the intrinsic capacitance was presented by Li et al. where the reduced graphene oxide
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of an individual graphene nanosheet. Different kinds of spacer and activated carbon composite was synthesized by a facile
DOI: 10.1039/C7TA02653F
materials could be employed to prevent the agglomeration of chemical method for the capacitive removal of salt ions from
graphene and increase the specific surface area of graphene. brackish water.223 In the reduced graphene oxide and
To exploit the potential electrochemical applications for activated carbon composite, reduced graphene oxide acts as a

graphene, many efforts have been focused on the composites flexible bridge to form a plane-to-point conducting network,
of graphene with other materials,89, 209 such as graphene- which is beneficial for decreasing the aggregation of activated
porous carbon composites, graphene-carbon nanotube carbon particles and therefore enhances the pore availability.
composites, graphene- activated carbon fiber composites, The electrosorption capacity of the composite electrode is 2.94
graphene-metal oxide composites, graphene-polymer mg g-1 in a NaCl solution with an initial conductivity of 0.1 mS
composites, and graphene-based multi-composites. cm-1 at 1.2 V.
2.2.1 Graphene-porous carbon composites for CDI. Porous Apart from activated carbon, carbon aerogel is another
carbons have been demonstrated to be an attractive material promising material for the CDI technology.224-227 Carbon
for CDI,210-212 since their unique porous structure with a high aerogels consist of interconnected, uniform carbonaceous
accessible surface area, low resistance, maximal structural particles (330 nm) with small interstitial pores (<50 nm). Such
stability and good chemical stability, which can facilitate ion a continuous, monolithic structure leads to a very high specific
transport and storage.213-215 Among porous carbons, activated surface area (4001100 m2 g-1) and good electrical conductivity
carbons stand out, together with its hybrid composite, are (25100 S cm-1).228-231
often utilized as a CDI electrode due to its high specific surface Interestingly, Pan et al. fabricated carbon aerogels
area, low cost fabrication, large-scale production and natural electrodes with reduced graphene oxide additive, in which
abundance.216-221 As a general trend, an increase in the total reduced graphene oxide was considered as a new kind of
pore volume/specific surface area results in a higher salt conductive additive.232 As a result, the surface of reduced
adsorption capacity.222 The graphene-activated carbon graphene oxide sheets is bestowed with a great deal of carbon
composites can not only increase the vacancies to aerogels. It is confirmed that a good contact between reduced
accommodate ions, but also speed up the transportation of graphene oxide and carbon aerogels is formed, which favors
ions to promote the ion adsorption due to the high specific the electron transfer between them. Apparently, the carbon
surface area (1000-3500 m2 g-1) of activated carbons and the aerogels electrode with 15 wt% reduced graphene oxide
superior conductivity (theoretically 7200 S m-1) of graphene. exhibits the highest desalination efficiency of 59% in a NaCl
A detailed study on graphene-activated carbon composites
Table 1 Comparison of the salt adsorption capacity among various graphene.
Specific Salt adsorption

Applied Initial NaCl Operational
Materials Preparation method surface area capacity Ref.
voltage (V) concentration mode
(m2 g-1) (mg g-1)
Graphene Hummers method 14.2 1.2 50 S cm-1 Batch-mode CDI 1.85 139
graphene-like
Hummers method 222.01 2.0 55 S cm-1 Batch-mode CDI 1.35 102
nanoflake
Graphene Pyridine thermal / 2.0 86.9 S cm-1 Batch-mode CDI 0.88 154
Three-dimensional
macroporous
Template-directed 339 1.6 105 S cm-1 Batch-mode CDI 3.9 195
graphene
architectures
Sponge-templated
Sponge -templated 305 1.5 106 S cm-1 / 4.95 191
graphene
Graphene sponge Freeze-drying 356.0 1.2 500 mg L-1 Batch-mode CDI 14.9 196
Microporous
KOH-activated 3513 2.0 160 S cm-1 Batch-mode CDI 11.86 198
graphene
Mesoporous graphene KMnO4 etching 474.0 1.2 500 mg L-1 Batch-mode CDI 14.2 204
Three-dimensional
graphene with Oxometalates
824 1.2 1045 S cm-1 Batch-mode CDI 14.7 207
hierarchically porous etching
structure
Holey graphene Home-made
H2O2 etching 1261.7 1.2 500 mg L-1 16.0 192
hydrogel CDI
Silica particles as Single Pass-
3D porous graphene 2680 1.4 300 mg L-1 14.08 208
templates Asymmetric-CDI

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solution with an initial conductivity around 100 S cm-1 at 1.2

V.
Although the activated carbons and carbon aerogels have
been the most widely used as CDI electrodes, the presence of
small micropores (<2 nm) always restricts the desalination
performance due to the limited ion accessibility and slow ion
diffusion. 101, 233-236 To solve this problem, mesoporous carbon

with a large accessible surface area, high and tunable
mesoporosity, and narrow pore-size distribution seems to be
an attractive candidate for CDI electrodes, which has been
demonstrated by us and other groups.26, 30, 32, 237 It is clear that
the mesoporous carbon has a much better electrochemical
performance than conventional high-surface-area activated
carbons in both aqueous and non-aqueous electrolytes.238-240
To exploit the potential electrochemical applications for
graphene, our group prepared graphene/mesoporous carbon
composites via a direct triblock-copolymer-templating method Fig. 12 (A) Schematic illustration of the procedure for the preparation of 3D
and used as CDI electrodes for the first time.241 A combination graphene frameworks-microporous carbon spheres composite. (B) TEM image of
of mesoporous carbon and graphene in this work opened a 3D graphene frameworks-microporous carbon spheres composite. (C)
new opportunity to prepare high surface area and highly Concentration transients of 3D graphene frameworks-microporous carbon
conductive carbon materials for CDI application. As for the sphere composite electrodes. The inset is corresponding electrosorption
graphene/mesoporous carbon composites, both mesopores capacities. (D) Cycling stability of 3D graphene frameworks-microporous carbon
spheres composite electrode. Copyright 2016, Elsevier Ltd.
and paper-like structures can be observed in Fig. 11A. The
specific surface area increases from 567.7 m2 g-1 for pristine
mesoporous carbon to a maximum value of 685.2 m2 g-1 for a promising electrode material due to its fascinating ion
graphene/mesoporous carbon composites. Of more concern is transportation with a smaller inner resistance and a shorter
that the introduction of graphene can improve the diffusion pathway.166, 242, 243 On the one hand, the carbon
desalination capability of the mesoporous carbon electrode to nanospheres acting as nanospacers were introduced into dual-
a large extent and the specific electrosorption capacity of the template method and investigated its CDI behavior for the first
graphene/mesoporous carbon composites and mesoporous time.244, 245 This revealed that the resultant electrode with a
carbon electrodes is 0.7 mg g-1 and 0.6 mg g-1 in a NaCl hierarchical pore arrangement exhibits superior CDI
aqueous solution with an initial conductivity of ~89.5 S cm-1 performance over the ordered mesoporous carbon one with a
at 2.0 V, respectively (Fig. 11B). The graphene/mesoporous single-sized pore channel. For example, Pan group reported
carbon composite electrodes were proved to be promising novel hierarchical hybrids with microporous carbon spheres
electrodes for CDI. decorated 3D graphene frameworks through a simple freeze-
Recently, the 3D hierarchically porous carbon combining drying process,246 which not only possess a unique
macropores, mesopores and micropores has been explored as hierarchically porous structure with micro-/meso-/macropores,
but also maintain favorable features for CDI applications (Fig.
12A and B). A high electrosorption capacity (9.86 mg g-1) was
obtained in a NaCl solution with an initial concentration of
~100 mg L-1 at 1.2 V (Fig. 12C). The electrosorption capacity
still maintains a high value of 19.01 mg g-1 after 30 times of
cycling, showing a good performance in durability and stability
(Fig. 12D).It is expected that the obtained composites will not
only serve as a highly efficient CDI electrode material, but also
hold the potential to be applied in other fields.
Furthermore, our group rationally designed graphene-
coated hollow mesoporous carbon spheres and originally used
as efficient electrode materials for CDI application199. The
Fig. 11 (A) TEM images of graphene/mesoporous carbon composites. (B) Comparison of
CDI curves of the activated carbon, mesoporous carbon and graphene/mesoporous
graphene-coated hollow mesoporous carbon spheres were
carbon composites electrodes. Copyright 2012, the Royal Society of Chemistry. fabricated by a simple template-directed method using
phenolic polymer coated polystyrene spheres as templates (Fig.

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Fig 13 (A) Schematic illustration of the fabrication of graphene coated hollow mesoporous carbon spheres. (B) TEM image of phenolic polymer coated polystyrene spheres. (C) TEM
image of graphene oxide coated the phenolic polymer and polystyrene spheres composites. (D) TEM image of graphene coated hollow mesoporous carbon spheres. Copyright
2014, the Royal Society of Chemistry.
13A). The resulting graphene-based composites have a enormous mesoporous channels has been successfully
hierarchically porous nanostructure with hollow mesoporous incorporated into the macroporous framework of 3D graphene,
carbon spheres uniformly embedded in the graphene sheets and the resultant composite displays a hierarchical pore
(Fig. 13B-D). The hierarchically porous structure of graphene- structure. The electrosorptive capacities were 6.18 and 4.41
coated hollow mesoporous carbon spheres electrodes can mg g-1 for the composite and pristine 3D graphene electrodes,
guarantee fast transport of salt ions, and the improved specific respectively. In addition, the desalination efficiency of the
surface area of graphene-coated hollow mesoporous carbon composite electrode can attain 88.96%, which displays an
spheres provides more adsorption sites for the formation of an evident improvement of 40% over the pristine 3D graphene
electrical double layer. In addition, the graphene sheets in the one (63.52%). The combination of 3D graphene and porous
graphene-coated hollow mesoporous carbon spheres as the carbon in the present work may open a new opportunity to
interconnected conductive networks lead to fast charge prepare a graphene-based hierarchically porous carbon
transfer. The CDI performance under a direct voltage of 1.6 V composite electrode with a higher specific surface area, an
was investigated. The electrosorption capacity of the enhanced electric conductivity, and a superior ion diffuse
graphene-coated hollow mesoporous carbon spheres pathway for CDI application.
electrode is calculated to be 2.3 mg g-1 in a NaCl aqueous Graphene-porous carbon composites, simultaneously
solution with an initial conductivity of 68.5 S cm-1. The combining wide porosities (micro-, meso- and macropores),
proposed carbon composite architectures are expected to lay has been regarded as a promising electrode material. On the
the foundation for the design and fabrication of high- one hand, porous carbon can prevent the aggregation of
performance electrodes in the field of energy and graphene and further increase the specific surface area. On the
electrochemistry. other hand, the incorporation of graphene with porous carbon
Another strategy to fabricate hierarchically porous graphene can speed up the ion diffusion by providing a decreased ion
is to introduce the porous carbon consisting of numerous diffusion distance and also ensuring a minimized inner
mesoporous and macroporous channels into the macroporous resistance for the ion transportation pathways. Besides, the
framework of 3D graphene to obtain a novel composite with a presence of porous carbon can serve as ion-buffering
3D hierarchical pore arrangement.247 The 3D graphene and reservoirs guarantees a shorter ion diffusion distance, which
hierarchically porous carbon composites were prepared by a facilitates the rapid transportation of the ions into the interior
dual-template strategy with SiO2 spheres as the hard template of the bulk material. Therefore, it is an effective method to
and the triblock copolymer Pluronic F127 as the soft one, and combine porous carbon with graphene to achieve high
the representative synthetic route is illustrated in Fig. 14. The desalination performance.
composite possesses macroporous and mesoporous structures 2.2.2 Graphene-carbon nanotube composites for CDI. Since
simultaneously. This indicates that the porous carbon with carbon nanotube have demonstrated significant

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Fig. 14 Schematic illustration of the synthesis route for 3D graphene and hierarchically porous carbon composite. Copyright 2013, the Royal Society of Chemistry.
electrosorption capacity in CDI, they could be an ideal spacer Analogously, Li and coworkers fabricated carbon nanotubes
for inhibiting the aggregation of graphene sheets and further coupled with reduced graphite oxide composite by a one-step
enhancing the desalination performance.248 In order to facile chemical method.260 The specific surface area of the
combine the merits of the 2D graphene and 1D carbon composite is given to be 438.6 m2 g-1. The electrosorptive
materials, many attempts have recently been made to obtain capacity of the composite is determined to be 1.4 mg g-1 in a
graphenecarbon nanotube hybrid materials or composites.249- NaCl solution with an initial conductivity of 1000 S cm-1 at an
258 applied voltage of 1.2 V. Besides, the charge efficiency of the
In order to inhibit agglomerates and increase the composite electrode at 1000 S cm-1 is lower than that at 100
conductivity in the vertical direction of the graphene, our S cm-1, revealing that CDI is envisioned to be a very energy
group employed carbon nanotube to intercalate graphene to efficient water desalination technology when the ionic content
form graphene and carbon nanotube composite architectures is relatively low.
by a modified exfoliation approach (Fig 15).259 In this carbon Another strategy to fabricate the carbon
architecture, long and tortuous carbon nanotubes as nanotube/graphene composite as electrodes for CDI was
conductive networks not only interconnect the adjacent explored by Zou et al.261 The structure of the carbon
graphene but also inhibit the aggregation of graphene. It was nanotube/graphene composite composite was highly porous,
found that with the carbon nanotube contents increasing, the with single-walled carbon nanotubes sandwiched between
specific capacitance of the electrodes firstly increases to the graphene sheets that functioned as spacers and provided
highest value and then decreases obviously. The graphene and diffusion paths for smooth and rapid ion conduction. The
carbon nanotube composite electrodes performed much associated increase in the electrical double-layer capacitance
better than the activated carbon and graphene ones in a NaCl enhanced the desalination performance. The carbon
aqueous solution with an initial conductivity of ~57 S cm-1 at nanotube/graphene composites achieved an electrosorption
2.0 V, and the salt adsorption capacity is 1.41 mg g-1 for the capacity of 26.42 mg g-1 with 100% regeneration in a 50 mL
graphene and carbon nanotube composite electrodes. The NaCl solution with an initial concentration of 780 mg L-1 (1540
graphene and carbon nanotube composites are confirmed to S cm-1 conductivity) at 2 V, showing great potential as a high
be promising materials for CDI electrodes. performance electrode material in CDI applications. To

Chemistry
carbon fibers and activated carbon clothes, have previously

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been developed as electrodes for capacitive deionization, due
DOI: 10.1039/C7TA02653F
to their high ratio of surface area to volume.263-265 Because the
ion adsorption efficiency of the carbon electrode can be
strongly dependent on the microstructure and chemical

functional groups formed during the chemical surface
modification, activated carbon cloths were chemically surface-
modified by etching in alkaline or acidic solution with various
etching time in order to improve the efficiency of CDI from
aqueous solution.266, 267
The electrospun activated carbon nanofibers webs exhibit
good monolithic structure and high electrical conductivity,
previous work has shown that activated carbon nanofibers
with various structure and multiscale texture hold promise for
CDI technology.268-272 The electrosorption capacity of the

activated carbon nanofibers composites can be further
improved by incorporating with graphene by electrospinning,
in which the graphene help to improve the electrical
conductivity and the pore distributions with tuned porous
structures.
For instance, Qiu et al. developed a new way to synthesize
web-like reduced graphite oxide and activated carbon
nanofiber composites by electrospinning, followed by CO2
Fig. 15 Schematic illustration of the formation process of graphene and carbon activation and applied to CDI.273 The as-made composites have
nanotube composites. Copyright 2012, the Royal Society of Chemistry. a well-developed mesoporous structure and high conductivity
that can be tuned to some extent by changing the weight ratio
increase the energy effectiveness and thus the of the mesoporous reduced graphite oxide incorporated in the
competitiveness of CDI, improved design, fabrication and electrospinning step (Fig. 17A and B). A high desalination
assembly of the CDI operational unit are equally important as capacity (7.2 mg g-1) and good reversibility for CDI of the
the development of high quality electrode materials. reduced graphite oxide and activated carbon nanofibers
Alternatively, Pan et al. designed and fabricated a novel composite were obtained at a low cell potential of 1.2 V in
graphene/carbon nanotubes hybrid sponge structures by comparison with the composite electrodes (Fig. 17C and D).
employing carbon nanotubes to intercalate graphene sheets in This approach may pave a new way to make web-like
a graphene sponge via directly freeze-drying graphene functional carbon materials with high performance for CDI
oxide/carbon nanotubes mixed solution followed by annealing desalination by incorporating reduced graphite oxide and
in nitrogen atmosphere (Fig. 16).262 The results show that activated carbon nanofiber composites under the further
graphene/carbon nanotubes hybrid sponge with 20 wt% optimized conditions.
carbon nanotubes has a maximum specific surface area of Qiu et al. fabricated the reduced graphene oxide/activated
498.2 m2 g-1. When used as CDI electrode, it exhibits a high carbon nanofiber monolithic composite web electrodes with
electrosorption capacity of 18.7 mg g-1 in a NaCl solution with tuned conductivity by using an ultrasound-assisted
an initial concentration of ~500 mg L-1 at an applied voltage of electrospinning method (Fig. 18A).274 Freestanding monolithic
1.2 V. carbon nanofiber webs function as a framework that prevents
As mentioned above, an ocean of great efforts have been graphene sheets from restacking. The conductive graphene
made to construct the graphene-carbon nanotube composites. network helps quickly transfer electrons across the matrix
The graphene-carbon nanotube composites can be obtained while the ions are efficiently stored in the pores of the
easily due to the - stacking interactions between graphene electrodes (Fig. 18B). As a result, a high electrosorption
and carbon nanotube. It has been demonstrated that the capacity for NaCl of 9.2 mg g-1 is achieved with an initial
intercalated carbon nanotubes can effectively exfoliate the conductivity of 300 mg L-1 of the NaCl solution at an applied
graphene and improve the conductivity, and enhance the
electrosorption eventually. Interestingly, the salt adsorption
capacity of the graphene-carbon nanotube composites ranged
from 1.4 mg g-1 to 26 mg g-1 under different test conditions. It
is because that the electrosorption capacity is related to
influent concentration, flow rate, voltage, and the CDI
equipment. Even so, the graphene-carbon nanotube
composite is quite a suitable and promising electrode material
for CDI electrodes.
2.2.3 Graphene-activated carbon nanofibers composites Fig. 16 Schematic illustration of the procedure for the preparation of graphene/carbon
for CDI. Commercial carbonaceous materials, such as activated nanotubes hybrid sponge. Copyright 2015, the Royal Society of Chemistry.

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Activated carbon nanofiber is considered to be a good
DOI: 10.1039/C7TA02653F
material in the water purification due to its large surface area,
moderate pore diameter and fast adsorption speed. The
incorporation activated carbon nanofiber into graphene can

increase the specific surface area and enlarge the conductivity
of the composite. Therefore, it is a great method to combine
the activated carbon nanofiber with graphene to enhance the
desalination performance.
2.2.4 Graphene-metal oxide composites for CDI. Graphene
and metal oxides are two hotspots as electrode materials for
many applications.275-280 The combination of these two types
of materials improves the specific capacitance largely due to
their synergistic effects. Therefore, such graphenemetal oxide
composites have also been explored in CDI applications.

Generally, the incorporation of metal oxide nanoparticles
like TiO2,281-283 MnO2,284-288 ZnO289-291, Fe3O4292, 293 and Co3O4294
Fig. 17 (A) Optical images of reduced graphite oxide and activated carbon
into some nanocarbon materials can inhibit the aggregation
nanofiber composites. (B) FESEM images of reduced graphite oxide and activated
tendency which can remarkably improve the specific
carbon nanofiber composites, the inset is the TEM image of reduced graphite
oxide and activated carbon nanofiber composites. (C) Electrosorption capacity of capacitance the incorporation of metal oxides will significantly
the activated carbon nanofibers, reduced graphite oxide, and reduced graphite improve the capacitance of graphene-based materials. The
oxide and activated carbon nanofiber composites electrodes as a function of metal oxide on carbon electrodes may contribute to the CDI
time in CDI. (D) Recycle electrosorption performance of the reduced graphite desalination efficiency with their suitable physicochemical
oxide and activated carbon nanofiber composites at a cell potential of 1.2 V. properties such as high hydrophilicity to increase the
Copyright 2014, Elsevier Ltd.
wettability of the electrode, inhibition of physical adsorption
of ion species affecting the electrochemical
charging voltage of 1.2 V (Fig. 18C). The micropores lead to an adsorption/desorption during CDI operation,295, 296 or
enhanced electrical double-layer capacitance while the alteration of the surface zeta-potential on the carbon
mesopores provide low-resistant pathways and channels for electrode to increase the ion removal rate.297
the ions through the porous fibers (Fig. 18D). The enhanced For example, Tang et al. presented a versatile method to
electrical conductivity of the composites by graphene addition fabricate 3D graphene aerogel/metal oxide (including TiO2,
(Fig. 18E) is another vital factor in improving electrosorption CeO2, Fe2O3, and Mn3O4) nanoparticle hybrids by using low
capacity. This study may provide new insights into high- valence metal ions as the precursors (Fig. 19A and B).298 The
performance, energy-efficient, and cost effective CDI. And also, incorporation of metal oxide remarkably improved the
it may be used as a basis of the wide applications of functional capacitance of graphene-based materials, and a high specific
reduced graphene oxide/activated carbon nanofiber
Fig. 18 (A) Schematic illustration of the electrospinning process coupled with ultrasonic spraying (B) Electrosorption capacity of the electrodes with different conductivities (C0=100
mg L-1, V=1.2 V); (C) Conductivity variation of the effluent and the corresponding current during 2.5 cycles, as measured in a batch-mode setup with a feeding NaCl solution (300
mg L-1) and 1.2 V applied voltage. (D) Schematic view of electrical double layer responsible for the electrosorption of ions. (E) Schematic of complex conductive network formed by
the incorporated graphene. Copyright 2016, Elsevier Ltd.

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capacitance of graphene aerogel/TiO2 hybrids was obtained. solution to the electrode through additional channels between
When the graphene aerogel/TiO2 hybrid with open pore graphene layers. The nanocomposite electrode has significant
structures used as the high performance CDI electrode electrochemical properties as it represents a remarkable
materials, the electroadsorption capacity of graphene increase in the specific capacitance. Even at low applied
aerogel/TiO2 reached to 15.1 mg g-1 in a NaCl solution with an potential (0.8 V), the reduced graphite oxide /TiO2 composites
initial conductivity of 500 mg L-1 at an applied voltage of 1.2 V has a high adsorption/desorption capability of ion salts (9.1 mg
(Fig. 19C and D). g-1) compared to pure reduced graphene oxide (1.89 mg g-1).
Among the commonly utilized metal oxides, TiO2 has the Additionally, the resulting composite electrodes exhibit
advantages of low cost, good chemical inertia, being eco- superiority in each of hydrophilicity, electrochemical behaviors,
friendly, and ease of anchoring into the carbon structure; desalination capacity and recyclability.
moreover it enhances the adsorption capacity in a CDI system. MnO2 as eco-friendly, low cost, and having good chemical
Compared to nanoparticulate morphology, nanorods exhibit stability and high capacitance is considered a promising
easier accessibility for ion adsorption due to the relatively candidate for many electrochemical applications. Most
large axial ratio aspect which offers higher ion accumulation recently, synthesis of the graphene/MnO2 nanocomposite has
and more interfacial contact.299 been reported as a high performance electrode for
To improve the electrochemical characteristics, El-Deen et al. supercapacitors301 and Li-ion battery302 applications using
proposed a green and efficient synthesis of reduced graphite different techniques including hydrothermal and traditional
oxide/TiO2 nanorods by using modified Hammer's method heating at high temperatures over many hours and multiple
followed by alkaline hydrothermal treatment for the prepared sequential steps.303 El-Deen et al. introduced a rapid and green
graphite oxide and TiO2 nanoparticles.300 The resultant TiO2 synthesis route for rapid transformation of graphite into
nanorods are fully encapsulated by graphene nanosheets. This graphene-intercalated with nanostructure MnO2 with
unique morphological structure reveals impressive features; morphology control by one-pot reaction, low-time consuming
high wettability, prevents releasing of TiO2, and creates and eco-environmentally method.304 Interestingly, morphology
superior facile accessibility of water and ions from the bulk
Fig. 19 (A) Schematic illustration of the formation mechanism of graphene aerogel/TiO2 hybrids (C) SEM image of graphene aerogel/TiO2 hybrids, inset in (B) is the image of the
monolithic graphene aerogel/TiO2 hybrids product after freeze-drying. (D) Desalination capacity of activated carbon, graphene aerogel and graphene aerogel/TiO2 hybrids with
different equilibrium concentrations and the corresponding Langmuir isotherm fitted curves; (E) Desalination efficiency of activated carbon, graphene aerogel and graphene
aerogel in 500 mg L-1 NaCl solution at different times. Copyright 2013, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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control could be performed; MnO2-nanorods and MnO2- ZrO2 is also considered a promising candidate due to its
nanparticles@graphene could be prepared (Fig. 20A). As an distinct characteristics such as eco-friendliness, inexpensive,
electrode in the CDI unit, the synthesized MnO2- good chemical stability, having a great ability for destroying
nanorods@graphene revealed distinct electrosorptive capacity some microorganisms attributed to its feature in
(5.01 mg g-1), amazing salt removal efficiency (~93%) and photocatalytic degradation of the organic pollutants,307
distinguished recyclability in a NaCl solution with an initial moreover it can enhance the adsorption capacity in the CDI
conductivity around ~100 S cm-1 at 1.2 V (Fig. 20B). system. Yasin et al. fabricated a graphite oxide/ZrO2 electrode
Therefore, the MnO2-NRs@graphene can be considered as with an easy manufacturing process via a simple hydrothermal
novel and efficient electrode materials for CDI applications. method.308 It is found that ZrO2 are successfully embedded in
The incorporation of metal oxides will significantly improve the graphene oxide sheets and enhances the conductivity of
the capacitance of graphene-based materials. Fe3O4, for graphite oxide plus provides a better storage space for ion
example, is environmentally benign, chemically stable and has adsorption and conduction. The obtained results indicated that
high pseudocapacitance through redox reactions. Potentially, the synthesized ZrO2-doped graphene oxide nanocomposite
Fe3O4 is a choice material for the synthesis of graphene/ metal having 10 wt.% ZrO2 exhibits great cycling stability, good salt
oxide nanocomposites for energy storage and related removal efficiency (93.03%), distinct electrosorptive capacity
technologies.305, 306 Li et al. prepared the reduced graphene (4.55 mg g-1) and high charge efficiency (0.84) in a NaCl
oxide and Fe3O4 hybrids by a facile hydrothermal method.293 solutions with an initial conductivity of 100 S cm-1 at 1.2 V. It
The resultant Fe3O4 nanoparticle is fully encapsulated by is believed that the graphene oxide could be considered a
reduced graphene oxide nanosheets and the specific surface good candidate as supporter material for capacitive
area of the reduced graphene oxide and Fe3O4 hybrids is 150.8 deionization attributed to its great theoretical surface area and
m2 g-1. Compared to the reduced graphene oxide, the good conductivity of graphene oxide.
enhanced capacitance of the reduced graphene oxide and The incorporation of metal oxides in the graphene-metal
Fe3O4 hybrids may arise from an exchange activity between oxide can prevent the aggregation of graphene, increase the
the hydrated Fe3O4 and Na+. When the RGO@Fe3O4 was wettability of the electrode, and improve the specific
fabricated as electrode for symmetrical CDI, it is found that the capacitance of the composite electrodes. As a result, the
removal capacity, electrosorption rate constant and charge desalination performance can be enhanced significantly. It is
efficiency of the reduced graphene oxide and Fe3O4 hybrids is worth mentioning that the external voltage should be
nearly twice as high as that of reduced graphene oxide due to controlled rationally to prevent to occurring the redox reaction.
the hydroxylation of Fe3O4 surface. Additionally, the maximum 2.2.5 Graphene-polymer composites for CDI. Similar to
removal capacity of the reduced graphene oxide and Fe3O4 metal oxides, a conducting polymer can contribute to the
hybrids is predicted by the Langmuir model, which shows a pseudo-capacitance,309, 310 which can largely enhance the
high value of 8.33 mg g-1 at 1.2 V in a NaCl solution with an capacitive performance of graphene for supercapacitor or CDI
initial conductivity of 500 S cm-1. applications.311-315 Among the wide range of materials that
may be suitable for the aforementioned applications, polymers
such as polyaniline, and polypyrrole,316-318 chitosan,319, 320 and
ion-exchange polymer321-324 are of particular interest.
Polyaniline is one of the most promising electrode materials
for pseudocapacitors due to its high specific capacitance and
electrical conductivity. And polyaniline has multiple redox
states, a high dopingdedoping rate during chargedischarge
and good environmental stability. Moreover, it can be
economically and easily fabricated into various
nanostructures.325-327 Polyaniline introduced in the
nanocomposite can enhance the capacitance of carbon
material, and at the same time the stability of polyaniline can
be improved by the carbon contained in the
nanocomposite.327-329 In the past years, composites of single-
walled carbon nanotubes and polyaniline have been studied as
Fig. 20 (A) Schematic illustration for the one pot synthesis procedure of MnO2-
the electrode material for CDI.330 The introduction of
nanostructures@graphene sheets as a sandwich structure. (B) CDI performance polyaniline modified the meso-structure of single-walled
of the synthesized materials electrode and activated carbon in the NaCl solution carbon nanotubes and facilitated the entrance and exit of ions
at 1.2 V. Copyright 2014, Elsevier Ltd.

Chemistry
electrospun porous carbon nanofiber webs would further

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enhance desalination capacity. This optimization can be
DOI: 10.1039/C7TA02653F
achieved by adding foreign materials (carbon black and carbon
nanotube, etc.) into polymer matrix, which has been
demonstrated by the improved physicochemical

characteristics of electrospun composite webs in studies for
various electrochemical applications.338-340 Huang et al.
prepared novel freestanding graphene oxide -embedded
porous carbon nanofiber webs by electrospinning from
polyacrylonitrile and graphene oxide, followed by
carbonization and steam activation.341 The graphene oxide-
porous carbon nanofiber webs possess nanometer-scaled fiber
diameter and improved hierarchical pore structure and
Fig. 21 (A) Schematic illustration of the in-situ polymerization of polyaniline in the electrical conductivity due to graphene oxide embedment,
presence of graphene sheets. (B) TEM images of graphene/polyaniline nanocomposite. which could lead to reduced ion-transport obstacle and
(C) Regeneration of electrodes performance. Copyright 2014, Elsevier Ltd. enhanced electrical double-layer capacitance. When the
graphene oxide-porous carbon nanofiber webs was used as
onto the surface of the electrodes. It was also reported that binder-free electrode in capacitive deionization, the
with graphite and polyaniline composite as electrode the CDI electrosorption capacities reached to 7.8 (C0 = 100 mg L-1) and
unit could be regenerated easily.331 13.2 mg g-1 (C0 = 450 mg L-1) at 1.2 V, respectively. More
For instance, Zou et al. synthesized the technical routes such as optimizing the percent of GO adding
graphene/polyaniline composites by chemical polymerization are still needed to enhance the desalination performance of
of aniline in the presence of dispersed graphene sheets nanofiber webs in further study.
through in-situ polymerization (Fig. 21A).332 The Wang et al. successfully synthesized the reduced graphite
graphene/polyaniline composite has a more homogeneous oxide-resol composite material,342 in which the reduced
pore distribution mainly in the range of 26 nm because of the graphite oxide is fully covered by resol. With the increase of
introduction of polyaniline (Fig. 21B). The ion removal voltage from 0.5 V to 2.0 V, the electrosorptive capacity
performance of the graphene/polyaniline composite was gradually rose from 0.457 mg g-1 to 1.424 mg g-1. With the
determined by using a membrane CDI bench-scale system. At concentration that increased from 25 mg L-1 to 65 mg L-1, the
500 S cm-1 initial concentration, conductivity removal was 94% electrosorptive capacity of the composite electrode is
for electrodes made of the graphene/polyaniline composite. In gradually enhanced from 1.424 mg g-1 to 3.229 mg g-1,
addition, faster regenerations of the graphene/polyaniline
nanocomposite electrodes were achieved at the initial
conductivity of 1000 S cm-1 at 1.2 V (Fig. 21C).
Polyaniline, as a conducting polymer, is one of the most
interesting materials due to its many advantages such as facile
in preparation, environmentfriendliness, chemical stability
and low cost production in large quantities.333, 334 Polyaniline
has a good processability when is blended with other polymer
such as polyvinyl alcohol, polyvinydene fluoride335 and
polyvinyl chloride 336, its solubility can be improved by
modification to form its derivatives. Therefore, Polyaniline
with good processability and solubility can be obtained by
chemical modification of the monomer.
In order to prepare more conductive ion exchange
membranes, Zou et al. fabricated a series of novel more
conductive anion exchange membranes by dry phase inversion
method, where the reduced graphene oxide/polyaniline was
added in the polyvinydene fluoride polymer matrix.337 The
prepared membranes possess both higher electrical
conductivity and high ion exchange capacity. More importantly,
it was found that adding the reduced graphene
oxide/polyaniline in the membranes formula has increased the
salt removal efficiency and sorption capacity. It was found that
sample with low graphene oxide concentration, and 50% Fig. 22 (A) Digital image of as-prepared porous Li+/graphene/carbon nanofiber. (B) SEM
polyaniline/reduced graphene oxide composites in the image of the as-prepared porous Li+/graphene/carbon nanofiber. (C) Sketch map of salt
membrane showed the best performance among all the adsorption and charge storage mechanism in porous Li+/graphene/carbon nanofiber
electrodes. (D) The desalination characteristics of porous Li+/graphene/carbon
membranes prepared.
nanofiber architectures and conventional active carbon particles plates in a CDI
Modifying the porous structure and electrical properties of
element with an initial concentration of 3.5%. Copyright 2016, Elsevier Ltd.

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possess the merits of different materials andView show good

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desalination performance. DOI: 10.1039/C7TA02653F
For example, Zhu et al. designed graphene/carbon
nanotube/activated carbon hybrids via a facile chemical
approach combing 2D graphene, 1D carbon nanotube with 0D

activated carbon into one new type of hybrids.344 This
hierarchical nanostructure is composed of a plane-to-line-to-
point (graphene-to-carbon nanotube-to-activated carbon)
conducting network. When used as a CDI electrode, the
composite exhibits a high electrosorption capacity of 10.94 mg
g-1 in a NaCl solution with an initial conductivity of ~1000 S
cm-1 at an applied voltage of 1.2 V. In addition, Niu et al.
presented a one-pot and one-step self-assembly process for
producing carbon sulfur electrode materials with a 3D
Fig. 23 (A) Schematic illustration for the synthesis of reduced graphene oxide interconnected structure, that is, a graphene/carbon
polypyrroleMnO2 (RGOPPyMn) composite. (B) SEM images of RGOPPyMn
nanotube/sulphur hybrid.345 Alternatively, Lou et al.
composites. (C) CDI profiles of reduced graphene oxide (RGO), RGOPPy0.5Cu1,
RGOPPy0.5Mn0.4, and PPy electrodes under 2.0 V. Copyright 2015, the Royal
demonstrated a facile one-step hydrothermal method is
Society of Chemistry. developed for large-scale production of well-designed flexible
and free-standing Co3O4 /reduced graphene oxide/carbon
nanotubes hybrid paper.346 Also, Zhang et al. synthesized Ag
illustrating that the initial concentration has a positive impact nanoparticlecarbon nanotubereduced graphene oxide
on electrosorption performance of reduced graphite oxide- hybrids by reduction of graphite oxide in carbon nanotube
resol composite. Compared with activated carbon and the as- graphene oxide hybrids and AgNO3.347 These graphene-based
synthesized reduced graphite oxide, this reduced graphite multi-composites are very useful for CDI application.
oxide-resol composite material can be a candidate of electrode, Another graphene-based multi-composites were prepared
which shows a promising potential for efficient CDI process in by Zhang and coworkers.348 The large-scale Li-ion doped
brackish water desalination and drinking water purification. graphene/carbon nanofiber porous architectures were
At the same time, Wang et al. applied the reduced graphite fabricated by electrospinning homogeneous LiNO3/graphene
oxide-resol composite as a CDI electrode for the removal of oxide/polyacrylonitrile nanofibers, followed by carbonization
ferric ions.343 The reduced graphite oxide-resol composite has at 900 C (Fig. 22A and B). The architectures show good
the largest electrosorptive capacity of 3.47 mg g-1 in FeCl3 electrical adsorption, which is enhanced by the incorporation
solution with an initial concentration of 40 mg L-1 and electrical of LiC6 and graphene with a higher electro-adsorption capacity
voltage of 2.0 V. For the reduced graphite oxide and activated and a faster adsorption rate due to the large surface area
carbon electrode, the electrosorptive capacities are 2.46 and (393.64 m2 g-1) and good conductivity. Li+/graphene/carbon
1.41 mg g-1, respectively. This is again confirming that the nanofiber electrodes have a higher electroadsorption capacity
composite is a suitable candidate as the electrode material for and a faster adsorption rate showing high electrical
CDI. The electrosorptive capacity of FeCl3, MgCl2 and NaCl adsorptionand a faster adsorption rate showing high electrical
were 3.41, 2.84 and 2.36 mg g-1, respectively, following the adsorption (the maximum efficiency =84%), which is
order Fe3+ > Mg2+ > Na+. The electrosorptive capacity of enhanced by the incorporation of Li-ion and graphene (Fig.
Fe2(SO4)3, Fe(NO3)3 and FeCl3 are 3.69, 3.58 and 3.41 mg g-1, 22C). A possible mechanism was proposed to explain the salt
respectively. The order of the anions removal efficiency was adsorption and charge storage in the Li+/graphene/carbon
SO42- > NO3- >Cl-. Besides, through investigation of the nanofiber electrodes according to modified Donnan model of
adsorptionelectrosorption kinetics, it is confirmed that the EDLCs theory.
electrosorption could effectively enhance the adsorption rate Recently, the incorporation of conducting polymers and
and adsorption capacity according to the adsorption transition metal oxide in some graphene-based materials to
electrosorption rate constant as a result of pseudo-first-order improve their capacitance has been remarkably
adsorption. investigated.349, 350 In the novel architectures with conducting
The capacitance and adsorption capacity of the composite polymer, graphene not only serves as a highly conductive
electrodes can be improved obviously by introducing the support material but also provides a large surface for the
conducting polymer in the graphene-polymer composites,. dispersion of conducting polymers.351 Additionally, the
Moreover, the graphene-polymer composites can reduce the introduction of conducting polymers can minimize
co-ion effects and improve the desalination performance due therestacking effects of graphene sheets as spacers, and
to the combination of ion exchange polymer with graphene. thus, the electrochemical performance of these composites is
2.4.6 Graphene-based multi-composites for CDI. Although enhanced to some degree accordingly.352 Among transition
the graphene-based composites exhibit high specific surface metal oxides, manganese oxide has stood out due to its
area or good electrical conductivity or favorable surface outstanding characteristics such as high theoretical specific
wettability, it is difficult to combine two or more advantages capacitance, natural abundance, and environmental
into the composites for the CDI electrodes. Therefore, the friendliness.286, 302, 353 Furthermore, constructing graphene
graphene-based multi-composites have been studied for CDI composite electrodes with manganese oxide can enhance the
applications. The graphene-based multi-composites usually

Chemistry
g-1 for the graphenechitosanMn3O4 composite was obtained,

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much higher than 6.5 mg g-1 for graphene and
DOI: 7.93 mg g-1 for
10.1039/C7TA02653F
graphenechitosan electrodes in a NaCl solution with an initial
conductivity of 300 S cm-1 at a working voltage of 1.6 V (Fig.
24C and D). The graphenechitosanMn3O4 composites

prepared by this green method can facilitate the fabrication of
suitable and promising materials for high-performance CDI
electrodes.
Apart from that, Estevez et al. reported the synthesis of
multifunctional hybrids in both films and bulk form, combining
electrical and ionic conductivity with porosity and catalytic
activity. The hybrids are synthesized by a two-step process: (a)
ice templation of an aqueous suspension comprised of Nafion,
graphite oxide, and chloroplatinic acid to form a microcellular
porous network and (b) mild reduction in hydrazine or

monosodium citrate which leads to graphene-supported Pt
Fig. 24 (A) Schematic illustration for the synthesis of graphene-chitosan and graphene-
nanoparticles on a Nafion scaffold.358 The graphene-based
chitosan-Mn3O4 xerogels. (B) SEM images of graphene-chitosan-Mn3O4 xerogels. (C)
CDI profiles of graphene, graphene-chitosan, and graphene-chitosan-Mn3O4 xerogel multi-composites can combine the advantages of various
electrodes under 1.6 V. (D) Electrosorption capacity and removal efficiency of materials together to achieve high desalination efficiency.
graphenechitosanMn3O4 xerogels electrode in a NaCl solutions with respect to Table 2 summarizes the salt adsorption capacity of various
different initial concentrations. Copyright 2015, American Chemical Society. graphene-based composites. In summary, graphene-porous
carbon composites, graphene-carbon nanotube composites,
electronic conductivity of manganese oxide with the aim of graphene-activated carbon nanofibers composites can prevent
improving capacitive performance. the agglomeration of graphene and increase the specific
For example, Wang et al. developed a 3D porous reduced surface area of graphene with enhanced desalination
graphene oxidepolypyrroleMnO2 composite, combining the performance. Graphene-metal oxide composites and
hydrothermal method with the chemical oxidative graphene-polymer composites can exhibit exciting
polymerization (Fig. 23A and B).354 The resultant composites characteristics, such as high electrical conductivity, enhanced
exhibit a hierarchically porous structure with a specific surface specific surface area, and high charge efficiency and
area of 331 m2 g-1 and good specific capacity of 356 F g-1, much desalination performance. The graphene-based multi-
higher than those of pure reduced graphene oxide or composites take full advantages of different materials to
polypyrrole electrodes. Enhanced electrochemical capacity and become good electrodes with high conductivity, large specific
low inner resistance endow the composite electrodes with an surface area, and good wettability.
outstanding specific electrosorptive capacity of 12.5 mg g-1 2.3 Surface tuned graphene and its composites for CDI
under 2.0 V in a NaCl solution with an initial conductivity of
Generally, the surface properties of electrode material, such
600 S cm-1 (Fig. 23C). Furthermore, the composite electrodes
as wettability, hydrophilicity and surface charge are critical in
have good rate stability and cycling stability for capacitive
determining the desalination performance. The surface-tuned
deionization applications.
graphene, including nitrogen-doped graphene and
Graphene/metal oxide composites are drawing increasing
attention to electrode materials since graphene not only functionalized graphene could show good wettability and high
serves as a highly conductive support material but also specific surface area, which is beneficial to improve the
provides a large surface for the dispersion of metal oxide desalination performance. Typically, doping heteroatom or
nanoparticles. Chitosan, derived from the alkaline grafting functional groups on the surface of graphene is an
deacetylation of chitin, has been intensively studied due to the effective method to tune the surface of the graphene. The two
properties of being environmentally friendly, low cost, and dimensional structure of sp2 hybridized carbon has great
available from an abundant source.355 Owing to a large potential due to its extraordinary physicochemical and
amount of primary amines along its backbone, chitosan electronic properties. Modification via chemical doping with
possesses useful properties including biocompatibility, hetero-atoms or charge groups can further improve the
biodegradability, and antimicrobial ability, especially metal ion electronic properties of graphene.359-362, Nitrogen-doped
adsorption activity.356 Gu et al demonstrated a green method graphene and functionalized graphene in particular, have
for the preparation of graphenechitosanMn3O4 composites, shown promise for high-performance CDI applications.363, 364
where graphenechitosan hydrogels are first prepared from
2.3.1 Nitrogen-doped graphene for CDI. Recently, nitrogen
the self-assembly of chitosan with graphene oxide nanosheets;
doping has attracted wide attention as an effective method to
then the composites are obtained by oxidizing Mn(II) ions
improve the electrochemical performance of carbon
which are adsorbed by graphenechitosan hydrogels (Fig.
24A).357 This unique 3D morphology and chitosan sheets materials.365-368 Doping of nitrogen atoms into graphitic
effectively prevent restacking of graphene sheets (Fig. 24B), networks is considered as one of the best approaches to
which can offer open a diffusion path for the efficient access of produce n-type conductive materials with improved
both charge and ions. The electrosorptive capacity of 12.7 mg conductivity.369 Up to now, different kinds of nitrogen doped
carbon materials, such as

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Table 2 Comparison of the salt adsorption capacity among various graphene-based composites
Salt adsorption
Specific surface area Initial NaCl Operational
Electrode material Applied voltage (V) capacity Ref.
(m2 g-1) concentration mode
(mg g-1)
Reduced graphene-activated carbon 779 1.2 100 S cm-1 Batch mode CDI 2.94 223
Three-dimensional graphene
frameworks with microporous 676.9 1.2 100 mg L-1 Batch mode CDI 9.86 246
carbon spheres
Graphene/mesoporous carbon 685.2 2 40 S cm-1 Batch mode CDI 0.73 241
Graphene-coated hollow
400.4 1.6 68.5 S cm-1 Batch mode CDI 2.3 199
mesoporous carbon spheres

Three-dimensional graphene-based
hierarchically porous carbon 384.4 1.2 60 S cm-1 Batch mode CDI 6.18 247
composites
Graphene aerogel/TiO2 187.60 1.2 600 mg L-1 Batch mode CDI 24.2 298
Reduced graphene/TiO2 658 0.8 560 S cm-1 Single-pass mode MCDI 9.1 300
MnO2-nanorods@graphene - 1.2 100 S cm-1 Batch-mode CDI 5.01 304
Reduced graphene @Fe3O4 150.8 1.2 500 S cm-1 Batch-mode CDI 8.33 293
Graphene oxide/ZrO2 1.2 100 S cm-1 Batch-mode CDI 4.55 308
Graphene/carbon
426.56 1.2 1000 S cm-1 Batch-mode CDI 10.94 344
nanotubes/activated carbon
Graphenechitosan Mn3O4 240 1.6 300 S cm-1 Batch-mode CDI 12.7 357
Reduced graphene oxide

331 2.0 600 S cm-1 Batch-mode CDI 12.5 354
polypyrroleMnO2
nitrogen-doped carbon nanofibers,370, 371 porous carbon precursors,385-388 hydrothermal treatment,389-391 CVD,392 and
spheres,372-374 carbon aerogel,375-377 and graphene378-382 have treatment with plasma393, 394 and flames.395, 396 The common
been developed to show an improved desalination methods used to prepare the nitrogen-doped graphene for CDI
performance. Actually, the nitrogen in the graphene is thermal treatment in an ammonia atmosphere
frameworks could improve the electrical conductivity383 and For instance, Pan et al. prepared nitrogen-doped graphene
the wettability of the interface between the electrolyte and via a thermal treatment of graphene oxide in an ammonia
the electrodes.384 As a result, the salt ions can be captured atmosphere.364 The nitrogen atoms have successfully doped in
easily by the electrode materials, and then accelerating the graphene backbone and the doping ratio is about 7.3%.
salt adsorption rate. Nitrogen-doped graphene are typically Nitrogen doping in graphene can efficiently prevent the
synthesized by thermal conversion with various nitrogen stacking between graphene interlayers by introducing nitrogen

Chemistry
functional groups, and thus results in much higher specific concentration, this sample with high specific View surface area
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surface area and pore volume. The nitrogen-doped graphene offers the potential to develop high DOI:performance
10.1039/C7TA02653FCDI
displays a high specific surface area of 358.9 m2 g-1 with a pore electrodes.
volume of 1.02 cm3 g-1. Due to the increased pseudo-capacitive Gu et al prepared nitrogen-doped graphene composites by
effect of nitrogen doping and the improvement of the the carbonization of graphite oxide and melamine

wettability of the interface between the solution and the formaldehyde, in which melamine formaldehyde was used as
electrode, the nitrogen-doped graphene possesses good nitrogen source.400 The obtained composites exhibited a
capacitive performance. The electrosorption capacity is hierarchically porous structure, with a specific surface area of
determined to be 12.8 mg g-1 in a NaCl solution with an initial 352 m2 g-1 and a high degree of nitrogen doping of 10.86%.
conductivity of 1000 S cm-1 at 1.2 V. This work demonstrated Their good electrochemical capacity with low inner resistance
that the nitrogen-doped graphene should be a promising and high reversibility endows the 3D nitrogen-doped graphene
candidate as electrode materials for CDI. composite electrodes with an outstanding specific
Similarly, Pan et al. prepared the nitrogen-doped graphene electrosorptive capacity of 21.93 mg g-1 at 2.0 V in a NaCl
sponge by directly freeze-drying graphite oxide followed by aqueous solution with the initial concentration of 1000 S cm-1.
annealing in ammonia atmosphere.363 Nitrogen-doped The 3D reduced graphite oxide and melamine formaldehyde
graphene sponges display a high specific surface area of 526.7 composites are well suited as high performance CDI electrode
m2 g-1 with a pore volume of 3.13 cm3 g-1, and high degree of materials and can be further investigated as promising
nitrogen doping of 8.5%. It was noted that the electrosorption electrode materials for cost effective, energy-optimised CDI
capacity of nitrogen-doped graphene sponge was 21.0 mg g-1 technology.
when the initial NaCl concentration is 500 mg L-1 at 1.2 V. Apart from the mentioned above, the nitrogen-doped
Furthermore, the charge efficiency of nitrogen-doped graphene prepared by using other nitrogen precursors are also
graphene sponge is 0.60. The nitrogen-doped graphene expected to be applied for CDI. For example, the nitrogen-
sponge electrode can be completely regenerated and reused doped graphene hydrogel was prepared through an effective
for over 30 cycles without any declination. It is expected that one-step solvothermal reaction by using o-phenylenediamine
this work provide a promising candidate as CDI electrode as a double-N precursor.402 The doping level of nitrogen
material for practical applications. reaches up to 7.7 atom%. Du et al. prepared nitrogen-doped
Another common strategy to fabricate nitrogen-doped graphene sheets by a simple process using 1% ammonia water
graphene for CDI is doping nitrogen in the graphene with solution as the reducing agent, nitrogen precursor and
various solid nitrogen precursors. Several types of solid solvent.403 The N content in nitrogen-doped graphene sheets
nitrogen precursors such as melamine,391 ployacrylonitrile,388 was 4.4%. Park et al. synthesized the 3D nitrogen doped
cyanamide,397 urea398 and sugar399 have been reported for reduced graphene oxide monoliths using graphene oxide and
obtaining nitrogen-doped graphene via pyrolysis with variable melamine through an ice-templated assembly.404 The nitrogen
outcomes. For example, Gu et al prepared nitrogen-doped content of around 6.2 at% in the nitrogen doped reduced
graphene by the carbonization of graphite oxide and melamine graphene oxide is predominant pyridinic N-type configuration.
formaldehyde, in which melamine formaldehyde was used as Lee et al. prepared nitrogen-doped graphene sheets by using a
nitrogen source.400 The obtained composites exhibited a simple hydrothermal reaction with graphene oxide and
hierarchically porous structure, with a specific surface area of hexamethylenetetramine.405 The prepared nitrogen-doped
352 m2 g-1 and a high degree of nitrogen doping of 10.86%. graphene sheets reduced by hexamethylenetetramine have
Their good electrochemical capacity with low inner resistance
and high reversibility endows the 3D nitrogen-doped graphene
composite electrodes with an outstanding specific
electrosorptive capacity of 21.93 mg g-1 at a direct voltage of
2.0 V in a NaCl aqueous solution with the initial concentration
of 1000 S cm-1. The 3D reduced graphite oxide and melamine
formaldehyde composites are well suited as high performance
CDI electrode materials and can be further investigated as
promising electrode materials for cost effective, energy-
optimised CDI technology.
Alternatively, Amiri and co-workers developed a promising
and efficient route to fabricate highly-crumpled, few-layered
graphene and nitrogen-doped graphene nanosheets by
exfoliation of graphite in the presence of liquid-phase using
microwave-assisted methods with cyanamide as nitrogen
source.401 The specific surface area of nitrogen-doped
graphene nanosheets after annealing under a nitrogen
atmosphere at 900 C was 1689 m2 g-1, and the electrosorption
capacity was 1.96 mg g-1 at 2.0 V with an initial NaCl
conductivity of 50 S cm-1. Although the electrosorption Fig. 25 Schematic representation of nitrogen-doped graphene, and three types of
nitrogen in nitrogen-doped graphene. Copyright 2012, American Chemical Society.
capacity of nitrogen-doped graphene is not very high at low

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high nitrogen (8.62%) content. These nitrogen-doped In recent years, nitrogen-doped graphene-basedView composites
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graphene with high nitrogen content can effectively improve combining the advantages of other materials can further
DOI: 10.1039/C7TA02653F
the wettability of the CDI electrodes, and then enhancing the improve the desalination performance. An alternative route
desalination performance. involves the incorporation nanoporous carbon or metal oxide
Our group also prepared the nitrogen-doped porous hollow with the nitrogen-doped graphene surface, leading to high

carbon spheres by using polystyrene spheres as hard specific surface area and good electrical conductivity. The
templates and dopamine hydrochloride as carbon and nanoporous carbon or metal oxide can not only be employed
nitrogen, and the nitrogen doping amount is 2.92%.406 The as a spacer material to avoid the agglomeration of graphene,
nitrogen-doped porous hollow carbon spheres electrodes but can also be easily modified with other functional groups
present a high salt adsorption capacity of 12.95 mg g-1 at a cell and metal (or metal oxide) nanoparticles which are included in
voltage of 1.4 V with a flow rate of 40 mL min-1 in a 500 mg L-1 the pores to broaden their applications.
NaCl aqueous solution. It has been demonstrated that the combination of porous
Analogously, Liu et al. reported a simple fabrication of carbon with graphene can enhance their performance in the
nitrogen-doped graphene hollow spheres by utilizing electrochemical applications. For example, Yin et al. reported a
polystyrene nanospheres as hard templates.407 Graphite oxide self-template strategy for the fabrication of 3D nitrogen-doped
and polyaniline is first layer-by layer assembled on polystyrene hierarchically porous carbon/graphene.408 The content of
nanospheres, and subsequently calcinated in nitrogen nitrogen is 11.3%. The as-prepared 3D nitrogen-doped
atmosphere to remove the polystyrene spheres template and hierarchically porous carbon/graphene offers good dispersion,
realize the carbonization of polyaniline. The resultant nitrogen- high specific surface area of 3108.7 m2 g-1 and electronic
doped graphene hollow spheres have a high nitrogen content conductivity of 3096 S m-1. These results demonstrate that the
of 8.7%. Parvez et al. reported a facile synthesis of nitrogen- 3D nitrogen-doped hierarchically porous carbon/graphene
doped graphene by immobilizing graphitic carbon nitride on electrode is a good candidate for CDI.
graphene sheets to form a carbon nitride graphene The ordered mesoporous carbons are universally used for
composite.397 The carbon nitride graphene composite is then the CDI application due to their advantages of large surface
subjected to thermal treatment at 800, 900, and 1000C, area, tunable pore structure, uniform and adjustable pore size,
leading to the decomposition of carbon nitride and thereby chemically inert nature, mechanical stability and good
introducing nitrogen moieties into graphene, resulting in conductivity.409 Song et al. in situ synthesized composites of
pyridinic nitrogen, graphitic nitrogen and pyridinic N+-O- (Fig. grapheme and nitrogen-doped ordered mesoporous carbon
25). In this way, nitrogen-doped graphene sheets with nanosheets by a triblock-copolymer assembly directly on
nitrogen content from 4.0% to 12.0% can be obtained by graphene oxide (Fig. 26).410 The strong interaction of nitrogen-
controlling the pyrolysis temperature. This nitrogen-doped doped ordered mesoporous carbon and graphene in the form
graphene is also a potential candidate for CDI. From the above of N-O bonding limits graphene aggregation. The resulting
descriptions, nitrogen-doped graphene has typically been composites with the nitrogen-doped ordered mesoporous
synthesised by thermal conversion with various nitrogen carbon mass content of 95% shows a high surface area (1569
precursors or annealing in NH3 atmosphere. High degree of m2 g-1) and good electronic conductivity. This
nitrogen doped graphene can be obtained by both methods. graphene/nitrogen-doped ordered mesoporous carbon
Therefore, the high desalination performance can be achieved nanosheet is an optional candidate for CDI application.
due to the high wettability and conductivity. Alternatively, Pan et al. fabricated a nitrogen-doped
2.3.2 Nitrogen-doped graphene-based composites for CDI. electrospun reduced graphene oxidecarbon nanofiber
.
Fig. 26 Schematic illustration of the general preparation process of graphene/nitrogen-doped ordered mesoporous carbon composites. Copyright 2016, Elsevier Ltd.

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Fig. 27 Schematic illustration of the synthesis of N-doped nanoporous carbon/graphene nano-sandwiches. Copyright 2015, the Royal Society of Chemistry.
composite via electrospinning by adding graphite oxide into a batteries427 and supercapacitors428 The diatomic doping can
precursor solution and subsequent thermal treatment under improve the specific capacitance largely and increase the
an ammonia atmosphere.411 The XPS analysis confirmed that electron transfer rate effectively due to their synergistic
the nitrogen content of nitrogen-doped graphenecarbon effects. In addition, the nitrogen-doped graphene combined
nanofiber composite is 8.3%. The enhanced performance of with metal oxides, such as Mn3O4,429 MnO2,430 TiO2431 Fe3O4432
the nitrogen-doped graphenecarbon nanofiber composite is shows good electrochemical performance. Therefore, these
ascribed to the nitrogen doping and the formation of an materials are promising candidates applied in the CDI.
effective plane-to-line conducting network in the composite, 2.3.3 Functionalized graphene for CDI. When the traditional
which facilitates the electron transfer and ion transport as well porous carbon materials were used as an electrode material
as increases the specific surface area. The specific surface area for CDI application, counter-ions (the opposite charge to the
of nitrogen-doped graphenecarbon nanofiber composites is electrode) in the solution are adsorbed onto the electrodes
greatly improved to 864.10 m2 g-1. The salt adsorption capacity and co-ions (the same charge as the electrode) are expelled
of nitrogen-doped graphenecarbon nanofiber composites is when an electric potential is applied between electrodes.433
3.91 mg g-1 in a NaCl aqueous solution with the initial This means that ion adsorption and desorption occur
concentration of 100 S cm-1 at 1.2 V. simultaneously in the pore volume of the electrodes, which
Actually, a novel nitrogen-doped porous carbon can be leads to higher energy consumption and lower charge
obtained by using a bimetallic based on ZIF-8 and ZIF-67 as the efficiency.94, 434 To address this issue, an effective strategy is to
carbon and nitrogen sources.412 The nitrogen-doped carbon graft ion selective groups on the electrode materials.435, 436 In
posesses a large surface area of 813 m2 g-1, a high N content of the past years, novel functional carbon materials such as
8.0%, high graphitization degree, and good wettability. If this activated carbon,437 carbon nanotubes,438-440 and graphene441-
449 have attracted significant interests for desalination because
kind of nitrogen- doped carbon was combined with graphene,
it could show good desalination performance. Wang of their high electrical conductivity and tunable surface
demonstrated an ultra-small zeolitic-imidazolate-framework properties and morphology.439 For functional carbon materials,
nanocrystal layer protected carbonization method to prepare the combination of superior electron mobility and highly
nitrogen-doped nano-porous carbon/graphene nano- accessible surface can significantly enhance the interfacial
sandwiches (Fig. 27).413 The resultant carbonanosheets charge transfer rate.450 In addition, sulfonated graphene with
revealed a high specific surface area (1170 cm2 g-1), good wettability is beneficial for CDI performance due to the
nanoporous structure and good electrical conductivity. It introduction of hydrophilic functional groups.451, 452 It has been
should be a good potential electrode material for CDI. demonstrated that the desalination performance can be
Table 3 summarizes the salt adsorption capacity among further enhanced by using asymmetric configurations with
various nitrogen doped graphene and its composites. Apart functionalized electrodes.453-456
from N-doped graphene, the S-doped graphene,414-416 B-doped In order to obtain graphene nanosheets with high specific
graphene,417, 418 N, S co-doped graphene419-423 and N, B co- surface area and good dispersion in aqueous solution, Zou
doped graphene,424 S, P co-doped graphene425 have been group developed a novel three-step reduction of graphite
widely investigated in the application of solar cells,426 lithium oxide to obtain graphene nanosheets with high specific surface

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Table 3 Comparison of the salt adsorption capacity among various nitrogen doped graphene
Salt
Specific
Nitrogen Applied Initial NaCl adsorptio
Doping surface Operational
Materials content voltage concentrati n Ref.
method area mode
(%) (V) on capacity
(m2 g-1)
(mg g-1)
Three-dimensional Carbonized
reduced graphene with
1000 S cm- 400
oxidemelamine melamine 10.8 352.0 2.0 1 Batch-mode 21.9
formaldehyde formaldehy
composites de
Thermal
Nitrogen-doped treatment 1000 S cm- 364
7.3 358.9 1.2 1 Batch-mode 12.8
graphene in ammonia
atmosphere
Thermal
Nitrogen-doped treatment
8.5 526.7 1.2 500 mg L-1 Batch-mode 21.0 363
graphene sponge in ammonia
atmosphere
Highly-crumpled Annealing
nitrogen-doped with 10.3 1689.0 2.0 50 S cm-1 Batch-mode 0.21 401
graphene cyanamide
Nitrogen-doped
Thermal
reduced graphene
treatment
oxidecarbon 8.3 864.1 1.2 100 S cm-1 Batch-mode 3.9 411
in ammonia
nanofiber
atmosphere
composite
area and good dispersion in aqueous solution.457 As shown in such as silicon which may dramatically decrease the electrical
Fig. 28, iron powders, as mild and environmentally friendly conductivity, Zou et al proposed the surface modification of
reducing agents, were used in partial-reduction of graphite graphene nanosheets by the controlled introduction of
oxide and then, sulphonic functional groups were introduced sulphonic functional groups to enhance the hydrophilicity of
on the surface of partially reduced graphene oxide. The graphene nanosheets-based electrodes.459 Similar to hydroxyl
negatively charged sulphonic group units can effectively and carboxyl, sulphonic group is also hydrophilic and has been
prevent the graphitic sheets from aggregating and enhance adopted to improve the dispersion of graphene nanosheets in
specific surface area of graphene nanosheets after further water in which the negatively charged sulphonic functional
reduction by hydrazine. The electrodes based on this kind of groups can effectively prevented graphene nanosheets from
graphene nanosheets achieved a NaCl removal efficiency of aggregating after the reduction and result in higher specific
83.4% and specific electrosorptive capacity of 8.6 mg g-1 with surface area. Zou et al. creatively investigated wettability and
outstanding regeneration capability. The findings of this its influence on graphene nansoheets as electrode material for
research prove that graphene nanosheets synthesised from capacitive deionization. By altering the hydrophilicity of
this multi-step reducing process can be applied as high- graphene nanosheets through controlled introduction of
performance electrodes in the CDI process. sulphonic groups, the water contact angle of graphene
The functional groups on the surface of carbon materials nanosheets is much reduced, indicating a better wettability.
have a significant effect on the interfacial charge transfer rate In order to overcome the co-ion effects and enhance the
and the wettability of the electrodes. Zou et al. have reported charge efficiency, our group rationally designed a novel ion-
the addition of silica into carbon matrix to improve the selective 3D graphene electrode by grafting sulfonic and amine
wettability of electrode material and increased the electrode functional groups on three dimensional graphene (Fig. 29).
capacity by up to 28%.458 Instead of adding a secondary phase These grafted groups can act as ion-selective functional

Chemistry
coatings, which can minimize the co-ions expulsion effect and View Article Online
increase the charge efficiency. In addition, they can increase DOI: 10.1039/C7TA02653F
the hydrophilicity and wettability of the electrode surface,
which is beneficial for ion transmission from the solution to
the electrode. The CDI performance of functionalized 3D

graphene was evaluated at various operating conditions by
asymmetric configurations assembled with different
combinations of the sulfonated, aminated and original 3D
graphene. The CDI performances of the flow-through capacitor
based on the ion-selective 3D graphene were improved in both
salt adsorption capacity and charge efficiency. The results
show that the capacitor exhibits a salt adsorption capacity of
13.72 mg g-1 in a 500 mg L-1 NaCl aqueous solution with the
flow rate of 40 mL min-1 at 1.4 V and the charge efficiency
reaches 0.85. The rationally designed ion-selective 3D

graphene electrode can improve desalination performance
and reduce co-ion expulsion effects. The graphene electrode Fig. 28 Schematic illustration of the multistep synthesis of well dispersed graphene.
Copyright 2012, Elsevier Ltd.
can also be modified by carboxymethyl cellulose as negative
charge (COO-2) and quaternary ammonium cellulose with
positively charged polyatomic ions of the structure (NR4+). El- efficiency by surface modification of the electrodes could be
Deen et al. fabricated the functionalized microporous realized by the treatment using anhydrous ethanol solution
activated graphene electrodes by this strategy.208 Their novel containing metal alkoxides (such as titanium oxide),460 nitric
asymmetric coated microporous activated 3D graphene acid,440, 461-463 potassium hydroxide,464 sulfuric acid,465
employs nontoxic water-soluble binder which increases the permanganate,466 hydrogen peroxide,467 and zeolite.468 All of
surface wettability and decreases the interfacial resistance and these activating agents can effectively functionalize graphene
moreover improves the electrode flexibility compared with electrode materials with oxygen-containing functional group
organic binders. The desalination performance of the or ion exchange group, which are beneficial to improve the
fabricated electrodes was evaluated by carrying out a single wettability of electrode, and then increase the desalination
pass mode experiment with asymmetric cells, and shows efficiency.
superior desalination performance, cycling stability, and 2.3.4 Functionalized graphene-based composites for CDI.
charge efficiency. As previously discussed, sulphonated reduced graphene oxide
In addition, an effective method to improve the desalination can be generally fabricated by three steps, including
Fig. 29 Schematic representation of sulfonation and amination of 3D graphene. The inset is the salt adsorption capacity and current response for capacitors 3DGR3DGR and
3DNGR3DSGR in a 500 mg L-1 NaCl solution at 1.4 V with a flow rate of 40 mL min-1. Copyright 2016, the Royal Society of Chemistry.

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pre-reduction of graphene oxide with sodium borohydride, as compared to that of the bare carbon fiber cloth electrode
sulfonation with the aryl diazonium salt of sulfanilic acid, and due to the ion selectivity characteristic of sulphonated reduced
postreduction with hydrazine.451 In order to further promote graphene oxide nano-sheets and a decreased interfacial
the electrosorption capacity, some researchers proposed resistivity (Fig. 30C). This work provides a large-scale
assembling sulphonated reduced graphene oxide with carbon production method to prepare a novel carbon electrode for
fiber. For instance, Li et al. prepared a carbon fiber cloth and high performance CDI which might favor the
sulphonated reduced graphene oxide composite by commercialization of the CDI technique in the near future.
electrophoretic deposition (Fig. 30A).469 The resulting Alternatively, Qiu et al. demonstrated a rational design of
composite shows a cross-linked nanotubular structure and the sulfonated graphene and carbon nanofibers composites by
individual carbon fiber is fully encapsulated by sulphonated making use of electrospun carbon nanofibers with
reduced graphene oxide nano-sheets, forming a cylindrical- hierarchically porous structure as substrates, while by
shell microstructure. The composite electrode exhibits introducing the sulfonated graphene with abundant negatively
improved charge efficiency (0.45) of more than twice as charged groups as a cation exchange membrane (Fig. 31A and
compared to that of the bare carbon fiber cloth electrode due B).470 It can be seen that a relatively uniform coating is
to the ion selectivity characteristic of sulphonated reduced successfully attached onto the coated part of carbon
graphene oxide nano-sheets and a decreased interfacial nanofibers, which can be distinguished by a clear visible
resistivity. Specifically, the salt removal efficiency of the boundary (Fig. 31C). Notably, the as-made sulfonated
composite electrode reached to 60% when the electrical graphene and carbon nanofibers composites can be tuned to
voltage was 1.4 V in a NaCl solution with an initial conductivity hydrophilic from hydrophobic and show dramatic
of around 500 S cm-1 (Fig. 30B). The composite electrode enhancements in electrochemical properties. In addition, for
exhibits improved charge efficiency (0.45) of more than twice
Fig. 30 (A) Schematic illustration of the preparation of carbon fiber cloth and sulphonated reduced graphene oxide composites by electrophoresis deposition and the SEM image of
graphite, sulphonated reduced graphene oxide, carbon fiber cloth and carbon fiber cloth and sulphonated reduced graphene oxide composite. (B) The electrosorptiondesorption
performance of the carbon fiber cloth and sulphonated reduced graphene oxide composite electrode in a NaCl solution with an initial conductivity of 500 S cm-1 by varying the
cell voltage from 0.6 to 1.4 V. (C) Removal capacity and specific charge with respect to the cell voltage. Copyright 2014, the Royal Society of Chemistry.

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DOI: 10.1039/C7TA02653F
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the CDI cells those are constructed with asymmetric electrode is in agreement with the Langmuir adsorption
electrodes of pure carbon nanofibers and sulfonated graphene isotherm model, which is absolutely different from that of
and carbon nanofibers composites (Fig. 31D), the sulfonated activated carbon. After the introduction of m-
graphene coating shows significant cation selectivity, resulting phenylenediamine or p-phenylenediamine functionalized
in typical electrosorption behavior of membrane capacitive graphene, the composite exhibited an electrosorption capacity
deionization with an enhancement up to 89% in the of 12.58 mg g-1, which is approximately about 2.37 times that
electrosorption capacity and 137% in the charge efficiency. of the activated carbon electrode (5.31 mg g-1). The enhanced
The novel approach may open up a new way to the electrosorption performance of the composite is ascribed to its
applications of functional graphene-based materials for high enlarged accessible pore diameter as efficient channel for fast
performance, energy-efficient, and cost-effective desalination. salty ions and lower charge transfer resistance. The good
Functionalized graphene in particular has recently been performance of this composite indicates that it can be a
regarded as a promising CDI electrode material. However, the promising candidate as an electrode material for CDI.
preparation of functionalized graphene-based on graphene The functional groups on the surface of graphene not only
oxide usually results in serious secondary pollution due to can prevent the aggregation of graphene sheets but also have
usage of highly poisonous chemicals, and thus still cannot a significant effect on the interfacial charge transfer rate and
meet the demand of practical application. It is feasible that the wettability of the electrodes. As a result, the desalination
environmentally-friendly activated carbon and small amounts performance and charge efficiency are much improved. In
of functionalized graphene can be combined rationally, and addition to grafting ion-selective functional groups on
used as CDI electrodes. Therefore, Song et al. rationally graphene, many chelating agents, such as ethylenediamine
designed a novel composite electrode by sono-assembling triacetic acid,472-474 diethylenetriaminepentaacetic acid,475
activated carbon/m-phenylenediamine or p-phenylenediamine ethylenediamine,476 polydopamine,477 chitin478, 479 can also be
functionalized graphene into inter-connected network used to founctionalize graphene, and applied to heavy metal
architecture for CDI application successfully.471 The ions adsorption. Maybe the graphene modified by chelating
functionalization of graphene can not only inhibit its tendency agents can be used to separate heavy metal ions from salt ions
to agglomerate, but also distinctly improve the by the CDI technique. Furthermore, the functionalized
electrochemical performance including conductivity. The graphene combined with other carbon materials can
electrosorption experimental data obtained for the composite effectively increase the desalination efficiency.
Fig. 31 (A) Schematic illustration of the three-step synthesis of sulfonated graphene; insets display the digital images of reduced graphite oxide and sulfonated graphene
suspension after standing for 1 week. (B) Schematic illustration of the dip-coating process; insets show the digital images of reduced graphite oxide and carbon nanofibers
composites and sulfonated graphene and carbon nanofibers composites. (C) FE-SEM images of sulfonated graphene and carbon nanofiber composites from top view with a coating
boundary. (D) Schematic of three CDI cells assembled by different electrode pairs. Copyright 2015, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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good wettability and desalination performance, but the

nitrogen doped graphene and functionalized graphene
3. Summary electrodes have decreased adsorption sites due to the block of
The CDI technology is receiving tremendous attention and pores by large molecules. Graphene-based composites
research interest in recent years due to its energy-efficient electrodes generally show better conductivity and large
andcost-saving advantages over traditional desalination surface area; however, the preparation methods are often
technologies. In this review, we have summarized the recent complicated. Advantages always seem to be accompanied by
progress made on graphene-based materials for CDI trade-offs in these different kinds of graphene-based
electrodes, with a specific focus on the fabrication methods, electrodes. Thus, there exists substantial room for stimulating
different kinds of porous structure, the conductivity, specific research and development of high-performance graphene-
surface area and wettability needed for graphene-based based materials for CDI applications.
electrodes, and their influences on the desalination
performance. The outstanding graphene-based materials for
CDI always possess suitable porous structure, high conductivity 4. Future prospects
and good wettability, which were beneficial to enhance the The CDI technology has tremendous growth over the last
desalination performance. decade. Particularly, the graphene-based materials have been
The current research has mainly focused on fabricating demonstrated as potential CDI electrodes. However, further
graphene-based materials with an innovative structure, and development is needed for high-performance CDI electrodes
modifying them with functional groups or doping them with that can simultaneously ensure high salt adsorption capacity,
heteroatoms. Although recent developments in graphene- high salt adsorption rate and high charge efficiency. Rationally
based materials for CDI appear to be extremely promising, designing the porous structures of CDI electrodes to form
there remain challenges for different types of electrode hierarchically interconnected porous microstructures and
materials for practical applications. For example, the micro- avoid the formation of dead volume or the collapse of the
and mesopores in graphene can increase the surface area and porous microstructures is an effective way to enhance
offer a plenty of adsorption sites. But some dead pores and desalination performance. Besides, it is significant to endow
without perfect pore interconnection will limit the graphene with high conductivity, good wettability, and high
improvement of salt adsorption capacity and rate. The 3D specific surface area by tuning the surface of graphene or
macroporous graphene can guarantee a short diffusion combine graphene with other materials. In addition, it might
distance. However, the accessible surface area and ion be an effective solution to develop a new way to overcome the
transport in the 3D macroporous graphene need to be co-ion effects and then increase the salt adsorption capacity.
improved due to the lack of micro- and mesopores. Therefore, Therefore, excavating the potential of graphene-based
it is quite necessary to introduce mesopores and micropores materials for CDI is needed.
into the macroporous framework of 3D graphene to construct In addition to fabricating high performance electrode
a hierarchically porous architecture. The ion-buffering materials, a unified system to evaluate the desalination
reservoirs formed in the macroporous channels can minimize performance of CDI is needed. It is noted that it is difficult to
the ion diffusion distances into interior pore surfaces. The compare the reported performances due to the inconsistent
presence of the mesoporous structure guarantees not only a performance evaluation methods with different device
large accessible surface area for ion adsorption, but also a low- configuration and operating condition. Therefore, uniform
resistant pathway for ion transport through the framework, standards for calculating performance of different electrode
which can endow the 3D hierarchical graphene with high salt materials should be established. In the conventional
adsorption capacity and fast salt adsorption rate. Thus, it has desalination evaluations, the capacity and rate of desalination
great significance to control pore size and construct 3D were separately provided at the specific condition, thus facile
hierarchical graphene for CDI. acquisition of the overall desalination performance is difficult.
In addition to reasonable porous structures, the Recently, the CDI Ragone plot of salt adsorption capacity
electrochemistry and surface physical properties are also quite versus salt adsorption rate is used as a new performance
important. While graphene-based electrodes exhibit high metric of CDI, which evaluates the desalination performance
electrical conductivity, and good mechanical flexibility, they taking into consideration both the capacity and rate. The CDI
have only moderate desalination efficiency due to limited Ragone plot could facilitate designing and optimizing the CDI
wettability that generally confines the effective transport and process, working as a comprehensive guide to evaluate
diffusion of salt ions. In contrast, nitrogen doped graphene and desalination performance.
functionalized graphene electrodes endow the electrodes Generally, the cost consideration is of key importance to

Chemistry
make CDI an affordable mass-market technology. At the Although there are many challenges remain to be settled, we
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moment, the production costs for graphene come down believe that graphene-based CDI will emerge as a widely used
DOI: 10.1039/C7TA02653F
gradually. Besides, there are more and more methods for technology in the application of desalination in the near future.
construction of porous structure with high conductivity and
good wettability. It has been demonstrated that graphene-

based materials exhibit high desalination performance. Acknowledgements
Compared to traditional desalination methods, the CDI The authors acknowledge the support of the National Natural
technology is low-cost and environmentally friendly. All these Science Foundation of China (U1462110). The authors would
favorable conditions make it possible for the application of like to thank all the students and collaborators who have
graphene-based materials to the CDI technology in practice. worked diligently to carry out the original experiments.
In conclusion, graphene-based materials for CDI have been
extensively explored. It has been demonstrated that graphene-
based materials will play an important and perhaps References
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We systematically summarized current progress on graphene-based materials for capacitive

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Graphene-based materials for capacitive deionization

DOI: 10.1039/x0xx00000x Dengsong Zhanga,*

method based on electric double-layer capacitors (EDLCs).14

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Fig. 1 Schematic illustration of the CDI set-up

2. The theory and instruments of CDI

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desalination.108 Hatzell et al. developed a new type of

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Fig. 10 Schematic illustration of the preparation of graphene hydrogels and the

areas (up to 778.5 m2 g-1).

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Table 1 Comparison of the salt adsorption capacity among various graphene.

Specific Salt adsorption

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solution with an initial conductivity around 100 S cm-1 at 1.2

diffusion. 101, 233-236 To solve this problem, mesoporous carbon

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carbon fibers and activated carbon clothes, have previously

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CDI technology.268-272 The electrosorption capacity of the

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