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journal homepage: www.elsevier.com/locate/carbon

High-yield graphene production by electrochemical

exfoliation of graphite: Novel ionic liquid
(IL)acetonitrile electrolyte with low IL content
}d Gyenge
Amin Taheri Najafabadi, Elo

Department of Chemical and Biological Engineering, Clean Energy Research Centre, The University of British Columbia, 2360 East Mall,
Vancouver, BC V6T 1Z3, Canada

A R T I C L E I N F O

A B S T R A C T

Article history:

Electrochemical exfoliation of graphite assisted by ionic liquids (ILs) has been proposed as a

Received 10 October 2013

high-throughput, green and scalable graphene production technique. Previous research has

Accepted 7 January 2014

focused on IL/water electrolytes with high IL content (from 1:0.1 to 1:1 IL/water volume

Available online 15 January 2014

ratios). Here, we introduce and investigate a novel IL/acetonitrile electrolyte with dramatically lower loads of ionic liquids (1:50 IL/acetonitrile vol. ratio). Our approach provides
three main advantages: cost efficiency due to low IL content, extended electrochemical stability in a non-aqueous electrolyte, and high exfoliation yield by effective anionic intercalation within the graphitic layers. Using iso-molded graphite rod as the anode, we achieved
up to 86% of exfoliation with the majority of the products as graphene flakes in addition to
smaller quantities of carbonaceous particles and rolled sheets. We also demonstrate by
Raman spectroscopy the beneficial sonication effect on improving the quality of the graphene-based products. Moreover, in contrast with previous literature, we prove that the electrolyte coloration during electro-exfoliation in the IL media is related to the occurrence of
diverse reactions involving the IL moieties and cannot be associated with different stages
of graphene formation. The cathodically generated species can also interfere with the anionic intercalation in the graphite anode.
2014 Elsevier Ltd. All rights reserved.

1.

Introduction

Graphene, as the rising star in the world of advanced materials, offers game-changing prospects for many key areas of
research including energy storage and conversion, biotechnology, novel electronic devices and so forth [14]. This twodimensional planar sheet of sp2-bonded carbon atoms is
among the most widely researched nanomaterials since its
isolation by Geim and Novoselov in 2004 [5,6]. Graphene has
a large theoretical specific surface area (2630 m2 g 1) [7], high
intrinsic electron mobility (200,000 cm2 V 1s 1) [8], high
Youngs modulus (1.0 TPa) [9], and thermal conductivity

(5,000 Wm 1K 1) [10], while showing noticeable optical

transmittance (97.7%) [11,12]. Nonetheless, the commercial
success of many proposed graphene-based applications is
still unproven and among a number of factors, the need to
competitively produce it in large quantities is a major impediment. The latter necessity created a veritable graphene synthesis rush leading to the blooming state of publications on
various graphene production techniques with associated rosy
promises.
Graphene sheets (GNs) in scalable top-down approaches
(i.e. exfoliation of graphitic structures to produce ultrathin
layers) are usually produced as a mixture of monolayers,

* Corresponding author: Fax: +1 604 822 6003.

E-mail address: egyenge@chbe.ubc.ca (E. Gyenge).
0008-6223/$ - see front matter 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carbon.2014.01.012

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bi-layers and multilayers (310 layers), in the form of irregularly structured flakes or flat (or folded) sheets [13,14]. GNs
can be also produced as buckyballs (fullerenes) or as 1 D
nanotubes [15,16]. However, a key challenge here is to overcome the resilient exfoliation energy of the graphites pstacked layers originated from the high cohesive van der
Waals energy (5.9 kJ mol 1 carbon) among graphene sheets
[17,18]. In fact, Geim and Novoselov developed a top-down approach so-called micromechanical cleavage to extract single sheets of atoms from three dimensional graphitic
crystals using scotch tape exfoliation [6]. Graphite as an
earth-abundant starting material for the top-down preparation of graphene offers a cost-efficient and environmentallyfriendly alternative to bottom-up nanocarbon synthesis (i.e.
growing graphene monolayers from carbon atoms). Other
top-down methods include wet-chemical synthesis (or electrosynthesis) from graphite intercalation compounds (GICs)
[1921], direct liquid phase exfoliation [22], and solutionbased chemical reduction of graphene oxide (GO) [23,24].
At present, chemical reduction of GO, obtained from
graphite oxide exfoliation, to graphene sheets has emerged
as a promising method due to its low-cost and mass production potential [19,2531]. Graphite oxide is usually synthesized through oxidation of graphite via concentrated
sulphuric acid, nitric acid and potassium permanganate
based on the Hummers method [32,33]. Although graphite
oxide and GO share some similar chemical properties (i.e. surface functional groups), their structures are different. GO is a
monolayer material produced by the exfoliation of graphite
oxide [30]. Several reducing agents are proposed for chemical
reduction of GO sheets including hydrazine [3437], and sodium borohydride [38,39]. Hydrazine, unlike other strong
reductants, is nonreactive with water and is suggested to be
the most effective in synthesizing ultrathin and fine graphene
nanosheets [30]. Throughout the reduction process, the
brownish GO dispersion in water turns black and the reduced
sheets begin to agglomerate and precipitate in the reaction
vessel [29,40]. Such trends in color changes and dispersibility
of the reduced GO (rGO) in water is rendered by the removal of
oxygen atoms from the GO sheets, making the final product
more blackish and less hydrophilic [30].
Nonetheless, GNs synthesis via GO reduction leaves a significant amount of oxygen impurities behind, resulting in
numerous lattice defects [41,42]. Thermal annealing of rGO
sheets is reported to lower the GN network defects [24,43],
and finding more effective routes for complete reestablishment of the GNs sp2-bonded structure is of great interest
[26]. Moreover, most of the reported chemical production
techniques use harsh oxidizers (e.g. H2SO4/KMnO4), and an
excess of organic solvents (e.g. dimethylformamide or tetrahydrofuran), which are not environmentally benign [26,44].
Besides, the successive reduction of GO sheets to graphene
typically requires a strong chemical reducer (e.g. hydrazine
or sodium borohydride), and high temperature heating in order to recover the graphitic structure [45]. Thus, sever safety
measures must be taken when large quantities of these
reducing agents are used, making the scale-up of the process
challenging [46]. A handful of environmentally friendly processes are available [47,48] to reduce GO to graphene either
by chemical or electrochemical pathways; however, an

59

integrated green approach to the synthesis of graphene has

not been extensively explored.
To address the above-mentioned issues, researchers have
utilized electrochemical methods as a part of the GN fabrication process in the past few years [20,21,4954]. In principle,
GN electrosynthesis employs an ionically conductive solution
(electrolyte) and a direct current (DC) power source to prompt
the structural changes within the graphitic precursor (e.g. rod,
plate, or wire) used as the electrode. This offers a number of
potential advantages including ease of operation and control
over the entire synthesis process, being more environmentally benign with elimination of harsh oxidizers/reducers, relatively fast fabrication rates, and high mass production
potential at ambient pressure/temperature. Presumably, direct exfoliation of the graphene sheets from graphite would
overcome the low electronic conductivity of graphene films
chemically reduced from GO derivatives [29,54].
Considering the limitation of water electrolysis in aqueous
electrolytes, non-aqueous solvents are generally employed to
provide a wide electrochemical window [21,5254]. Among
those, ionic liquids have exhibited remarkable tendency to intercalate graphitic electrodes and yield gram-scale quantities of
carbon nanostructures (CNS) and GNs [20,54]. Air- and moisture-stable room temperature ionic liquids (RTILs), salts of large
organic cations with relatively bulky inorganic counter-ions, are
molten salts with melting points close to room temperature
[55,56]. Owing to low vapor pressure, high chemical and thermal
stability, solvating capability, non-flammability with potential
recyclability, RTILs have received pronounced interest as green
solvents in organic synthetic processes to replace classic, toxic
and volatile molecular solvents [57,58].
Due to the interdisciplinary nature of IL-assisted graphene
electrosynthesis, relatively little attention has been paid to
the reactivity of RTILs [59,60], and their unusual optical properties accompanied by a complex electrochemical behavior
[61,62]. Recently, the reactive nature of some specific RTILs
has been discussed by several research groups [6365]. Accordingly, the possible utilization of RTILs as catalysts or reagents,
besides their application as mere solvents, has been proposed
[56,60,66]. The concept of employing co-solvents to modify ILs
physicochemical properties [67,68], and the inevitable water
presence, coupled via hydrogen bonding with ILs anion
[69,70], are among other factors that induce more complexity.
The first published work on graphene electrosynthesis
using ILs goes back to 2008 when Liu et al. reported production
of functionalized GNs with 1:1 IL/water volume ratios [53].
They applied 1015 V to an electrochemical cell with graphitic
anode and cathode; where the exfoliation was observed at the
anode. This line of research was then pursued by Lu et al.,
focusing mainly on the complementary role of water during
the exfoliation process [54]. The latter authors showed that
replacing the graphitic cathode with a platinum wire does
not affect the electrosynthesis since the main processes
related to GN electrosynthesis occur solely at the anode. Furthermore, they attributed the wide range of produced nanostructured carbon materials to the fine tuning of the IL/water
ratios. In addition, the fluorescence behavior of the product
solution was assigned to the presence of carbon nanostructures. Ultimately, they suggested IL/water ratios of 1:0.1 for
the maximum production of sheet-like structures [54].

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Importantly, none of the aforementioned studies discussed nor defined the yield for GN electrosynthesis for the
various types of employed ILs and different IL/water ratios.
Thus, it is uncertain how practically feasible the electrosynthesis process could be for the production of specific nanostructures. Another aspect that has been previously
neglected is related to the possible parasitic reactions of the
IL molecules on the electrode surface. The adsorption, intercalation and possible electrode reactions of the IL moieties
can have a major impact both on the exfoliation process
and the overall efficiency.
In this research, we introduce and investigate a non-aqueous electrolyte composed of IL and acetonitrile with dramatically lower loads of ionic liquids (1:50 volume ratio)
compared with previously reported water-based systems. By
carrying out pertinent control experiments, we also reveal
the background electrode processes involving IL moieties that
could interfere with the anodic exfoliation process yet were
neglected in previous studies.

2.

Materials and methods

Fig. 1 shows the schematic of the experimental setup used for

graphite electro-exfoliation in the presence of ionic liquid
electrolytes. High purity iso-molded graphite rod (6.35 mm
diameter with 4 cm effective length exposed to the electrolyte, Graphite Store) was used as the anode with a platinum
wire as the counter-electrode (1.6 mm diameter and 4 cm
effective length). As electrolyte, both IL/water solutions and
the newly proposed IL/acetonitrile were tested (15 ml total
volume in each trial), at constant voltage of 7 V (B&K Precision-9110 DC power supply), and room temperature (293 K).
The passed current was 100 mA for all the cases with slight
decrease in the course of experiments. In our main trials,
0.1 M ionic liquid solutions in acetonitrile were used as the
electrolyte (1:50 IL/solvent volume ratio). It should be noted
that depending on the IL type, the exfoliation could happen at
lower potentials as well (e.g. 5 V). However, the operating conditions were fixed at the previously mentioned levels for the
sake of consistent comparison between different electrolytes
during 4 h of synthesis. The extent of graphite anode

exfoliation was evaluated by measuring the electrode volume

changes. This variable was used to quantify the exfoliation
yield in the presence of different ILs. The exfoliation solid
products were washed with copious amounts of water and
ethanol followed by separation by filtration and ultracentrifugation with rotational speed of 104 RPM at 20 C. Sample suspensions in N-methyl-2-pyrrolidone (NMP) were sonicated for
1 h to reach stable suspensions using a VWR Scientific tabletop ultrasonic cleaner (B3500-MTH). All the chemicals were of
the analytical grade, and double-distilled water was used during all of the preparation steps.
Iso-molded graphite is the iso-statically cold-pressed
graphite that guarantees uniform properties in all grain directions [71]. This differs from extruded graphite, which is
pushed through a die and has varying properties within its
structure. There is also no binder used in the manufacturing
process which enables more facile flake detachment upon
electro-expansion. It is our observation that in some previous
studies, ill-characterized graphitic precursors are employed
such as pencil lead. The latter is one of the most unreliable
choices since a typical 9B lead consists of more than 20 compounds including clays and binders, along with undefined
graphitic phases, that differ among various manufacturers
[72]. This significantly undermines the reproducibility of the
results when pencil lead is used as the working electrode
(i.e. graphene precursor).
As for the investigated RTILs, Fig. 2 shows the four types
tested in this research along with their electrochemical stability on platinum electrode at 293 K. The electrochemical window data was provided by the supplier (Iolitec Company)
and it was double-checked by us to reassure the accuracy.
These candidates noticeably possess high ionic conductivity,
electrochemical stability, non-inflammability, and very low
vapor pressures, making them an ideal medium for a vast array of syntheses. We selected them in a way to afford the evaluation of the roles played by different anions and cations
during graphene electrosynthesis. Compared to Fig. 2, most
of the previous researchers have examined only imidazolium-based ILs [53,54]. Furthermore, to lower the IL loading in
the electrolyte, it was dissolved in acetonitrile with 1:50
volume ratio (0.1 M). It is noteworthy that acetonitrile is

Fig. 1 Experimental setup used for graphite anodic exfoliation in the presence of ionic liquids. (A color version of this figure
can be viewed online.)

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61

Fig. 2 Investigated ionic liquids and their respective electrochemical stability windows on platinum at 293 K versus normal
hydrogen electrode (NHE).

commonly used as a nonreactive solvent for ionic liquids

especially in supercapacitors as it assures remarkable ionic
transport and conductivity while preserving the electrochemical stability window of the RTILs [73,74].
As for product characterization, transmission electron
microscopy (TEM) images were obtained with a Tecnai G2
microscope at acceleration voltages of 20200 kV. TEM grids
were covered with 5 microliters of the diluted products in
water/isopropanol mixtures to provide more facile evaporation and product visibility in imaging. Field emission scanning electron microscopy (FESEM) was performed using a
Hitachi S-4700 FESEM at 330 kV. X-ray photoelectron spectroscopy (XPS) was done by a Leybold Max200 for the surface
elemental composition and binding energy analysis with five
channeltrons, using an unmonochromated Mg Ka X-ray
source (1253.6 eV). A Micromeritics surface area analyzer
(ASAP2020) was utilized to determine the specific surface area
of the electro-exfoliated flakes. The fluorescence spectra of
the diluted electrosynthesis solution in water were collected
using a Varian Eclipse fluorescence spectrophotometer. The
Raman spectra were recorded via a LabRAM ARAMIS microscope Raman spectrometer with an argon-ion laser at an excitation wavelength of 632 nm. The samples deposited on
aluminum substrates were exposed to the laser beam (1 lm
diameter at the focus) with the exposure time of 1 s. The data
was collected from 3 to 5 different regions of each sample to
ensure the consistency of the results. All the measurements
were taken at room temperature without special mention.

3.

Results and discussion

3.1.

Electrosynthesis experiments

According to Lu et al., the GNs synthesis process by ILs electro-intercalation can be monitored based on the color
changes of the electrolyte [54]. They used BF4- as the anion
with an imidazolium-based cation similar to EMIM (Fig. 2,
left). Furthermore, these authors claimed that the specific
solution colors can be assigned to different categories of products generated including fluorescent carbon nanostructures
and graphene sheets [54]. In Fig. 3, we compare the color
changes during different stages of graphite electro-exfoliation
using EMIM BF4 (Fig. 3a) with control electrolysis experiments

where the graphite electrode was replaced by platinum wire

with a similar electrolyte (Fig. 3b).
Lu et al. proposed a three-stage color change classification
[54], which is in good agreement with our images shown in
Fig. 3a. They speculated that in stage I, there is an induction
period before visible signs of exfoliation can be detected. In
stage II, the electrolyte color changes from colorless to yellow
and then dark brown which is accompanied by a visible
expansion of the graphite anode (Fig. 3a). Finally, in stage
III, the expanded flakes peel off from the anode and form
the black slurry with the electrolyte [54]. However, nearly
identical color changes were observed in the control experiment, where we replaced the graphite anode with a platinum
wire and repeated the electrolysis under exactly the same
conditions (Fig. 3b). Therefore, clearly the color changes cannot be used as an indicator of various carbon nanostructure
formation suggested by Lu and coworkers [54]. Evidently, different color changes are solely originated from IL interaction
with the electrode surface (Pt or graphite).
In fact, one of the key properties of the imidazoliumbased RTILs, the most extensively studied class of ionic
liquids, is their Brnsted acidity [75] related to the C-2 hydrogen of the 1,3-dialkylimidazolium cation [62]. The electrochemical reduction of the C-2 proton initiates H2 evolution
at the cathode. This reaction also leads to the formation of
the electro-generated N-heterocyclic carbenes (NHCs) and
their derivatives via subsequent chain and/or decomposition
reactions [59,61,76]. Therefore, these species are
mainly responsible for the solution coloration (Fig. 3). NHCs
are highly reactive, as base/nucleophile, and can also react
with the graphite anode (see Section 3.2, XPS analysis
results).
In addition to the visible color changes of the electrolyte,
another discussion has emerged with respect to the fluorescent nature of some of the carbon nanostructures (e.g. nanoparticles and bucky gels) produced during electrosynthesis
[54]. Lu et al. described the obtained spectra of the alleged
fluorescent carbonaceous particles as generally broad and
excitation-wavelength-dependent; attributed to the size heterogeneity and distribution of different emissive sites on the
carbon nanoparticles [54]. This false presumption can also
be objected by comparing the fluorescence spectra of the
electrolyte solutions obtained from the two parallel
electrolysis experiments, with and without graphite anode,

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(a)

(b)
Fig. 3 Electrolyte color changes during (a) electrochemical graphite exfoliation, and (b) control electrolysis experiment
without graphite electrode in 0.1 M EMIM BF4/acetonitrile solution at 7 V and 293 K in the course of 4 h (anode is on the left
side in all images). (A color version of this figure can be viewed online.)

respectively (Fig. 4a and b). When the final solutions from the
two sets of experiments (a and b) were analyzed in a fluorescence spectrophotometer, they both exhibited similar excitation and emission trends (Fig. 4).
As mentioned earlier, another complexity of studying
RTILs, especially in the case of imidazolium-based cations,
is their unusual optical properties in the ultraviolet (UV) and
near visible regions [77,78]. Imidazolium containing ILs exhibit significant UV absorption, which extends into the early
part of the visible region. Their fluorescence trend covers a
large portion of the visible domain characterized by a significant excitation-wavelength-dependence. Such shifts of the
fluorescence maximum peaks are attributed to the various
associated structures present in the ionic liquids and the
incongruous excitation energy transfer process among them
[77,78]. In general, wavelength-dependent fluorescence
behavior of the organized assemblies such as membranes,
proteins and RTILs is observed when their dipolar moieties
get excited at the red edge of the absorption band, so-called
red-edge effect (REE) [79,80]. The described optical abnormalities become more severe under electrosynthesis conditions
where NHCs instigate a series of side reactions and further
affect the unusual excitation wavelength-dependent
tendencies. Thus, the complex fluorescence behavior of the
IL-containing solutions, especially under electrolysis
conditions, undermines any direct connection between the
fluorescence spectra and release of various carbon nanostructures to the solution during electrosynthesis.
As shown in Fig. 5, we next carried out parallel experiments using the four ILs illustrated in Fig. 2 to assess the
influence of the IL structure on the graphite electrochemical

exfoliation. In Fig. 5, first it can be observed that the solution

coloration cannot be correlated with the graphite exfoliation
yield. In other words, as shown in Fig. 5, about 86% of the
graphite electrode was exfoliated when BMPyrr BTA was used
as IL, while the final solution remained virtually colorless.
Conversely, when the exfoliation rate was at the lowest
(29%), in the case of EMIM BF4, the solution coloration was
the most severe, as discussed previously in relation to Fig. 3.
Furthermore, it is important to note that no color change of
the solution does not imply that the IL remains unchanged
during the electrosynthesis process. In the case of BMPyrr
BTA, where over 85% of the graphite anode peeled off with
minimum solution coloration, we still witnessed gas evolution at the Pt cathode; probably due to the cathodic decomposition of BMPyrr into methylpyrrolidine and a butyl radical
with its subsequent disproportionation leading to gaseous
product species formation [81].
The low exfoliation rate in the presence of EMIM BF4 can
be explained by the strong adsorption of EMIM on the cathode
surface followed by the electrode reaction leading to the formation of NHCs and subsequent chain reaction products.
These species formed at the cathode dissolve back to the
solution and can re-adsorb on the graphite anode, in competition with BF4-, hindering the BF4- adsorption and intercalation into the graphite layers. Thus, its inferred that the
cathodic by-products are hampering the anodic graphite
exfoliation. This hypothesis is further supported by the experiments using the same anion while changing the cations,
where a dramatic improvement in exfoliation rate was
obtained with minimum coloration in the case of pyrrolidinium-based cations (Fig. 5).

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63

Fig. 4 Fluorescence spectra comparison of the resulting electrolyte from (a) graphite electro-exfoliation experiment, and (b)
control experiment both in 0.1 M EMIM BF4/acetonitrile solution at 7 V and 293 K after 4 h. (A color version of this figure can be
viewed online.)

Fig. 5 Color changes and the exfoliation yield after 4 h of

ionic-liquid-assisted electrochemical graphite exfoliation at
7 V using 0.1 M IL/acetonitrile (1:50 IL/solvent vol. ratio) at
293 K (the shows 95% confidence interval from 3
experiments). (A color version of this figure can be viewed
online.)
Switching from BF4- to more oxygenated anions such as
bis(trifluoromethylsulfonyl)imide (BTA) increases the extent

of complexities but also enhances the exfoliation yield

(Fig. 5). Fig. 6 demonstrates how the initial brownish exfoliation of the graphite anode in the first 15 min is followed by
an intense blackish flake precipitation during four hours of
electrosynthesis. Due to the oxygenated nature of the BTA anions (Fig. 2), there is a higher chance of reactivity with the vulnerable sites of graphite anode. Similar impact was reported
during graphite exfoliation with SO42 intercalation [50]. We
concluded again by control experiments utilizing only platinum electrodes that the mild coloration of the electrolyte observed in Fig. 6 after 2 h is originated from the products of the
BMPyrr BTA electrode reactions such as cathodic reduction
followed by chain reactions and re-adsorption of the products
on the anode.
In the previous studies, there has been an overemphasis
on the critical role of water in water-based IL mixtures
[53,54]. Thus, it is necessary to make a few comments based
on our own experiments. First of all, no notable exfoliation
was observed with equivalent IL/water ratios compared to
that of the newly introduced IL/acetonitrile systems
(1:50 volume ratios). Thus, in order to induce any electroexfoliation in the water-containing systems much higher IL
content is necessary (e.g. 1:0.11 IL/water vol. ratios [53,54]),
which substantially increases the cost of the entire process.
Furthermore, high water contents significantly narrow the
electrochemical stability window, thus reducing the exfoliation power of the anionic intercalation compounds. On the
other hand, the water presence in RTILs is inevitable as most
of the ionic liquids are hygroscopic [82,83]. However, such
water traces are rapidly removed by the electrode reactions

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Fig. 6 Progressive exfoliation of the graphite anode in the BMPyrr BTA during 4 h with 0.1 M IL/acetonitrile at 7 V and 293 K.
(A color version of this figure can be viewed online.)

during electrolysis in the IL/acetonitrile electrolyte and will

not have any long-lasting impact. Therefore, water presence
is unnecessary for the electrochemical graphite exfoliation.
Instead, we proved that other co-solvents such as acetonitrile
that preserve the ILs potential window serve as much more
advantageous alternatives by affording the dramatic lowering
of the IL content with high rate of exfoliation.

3.2.

Products characterization

After 4 h of electrosynthesis, the exfoliated precipitates were

collected and thoroughly washed using deionized water and
ethanol. The solid products were then separated by filtration
and ultracentrifugation followed by drying in a vacuum oven
for 24 h at 85 C. The dried products were subjected to one
hour sonication in NMP. Fig. 7 shows the corresponding transmission electron microscopy (TEM) and field-emission scanning electron microscopy (FESEM) images. Depending on the
sampling depth and duration, we were able to capture a variety of structures from ultrathin graphene flakes (Fig. 7ad) to
semi-transparent carbonaceous particles (Fig. 7e), and rolled
sheets (Fig. 7f). After taking 250 TEM and SEM images of more
than 15 samples, we inferred that the majority of the produced materials are of the ultrathin irregularly shaped sheets
rather than the other described morphologies. Based on our
statistical analysis of the TEM images, the average length of
the flakes was in the order of 500 nm. In terms of thickness,
according to Meyer et al. [84] the folding fashion of the edges
is an important indication for the number of layers. Therefore, from the folded edges shown in Fig. 7b and c, formation
of monolayers and bilayers is inferable. Moreover, we did not
notice any major deviation from the planar topographies to
other described by-products when various IL structures were
employed for the synthesis.
Nonetheless, it is oversimplification to assume that the
rigorous electro-intercalation of energetic IL anions only leads
to planar morphologies. Isolation of the particles and rolled
sheets, even in trace amounts, which was successfully
achieved in our work certainly sheds some light on the exfoliation mechanism. Presumably, the initial anionic intercalation/expansion poses a strong mechanical stress on the
vertices and edges of the graphitic precursor which ultimately
results in breakage of the vertices (i.e. particle formation) and
bending the edges (i.e. rolled sheet formation). It should be
noted that such structures were separated in trace amounts

from filtration and centrifuge disposals, which might be typically overlooked by the researchers. Thus, we believe reporting these morphologies is a significant step towards
conducting more detailed studies in the future and is out of
the current focus of this paper.
Raman spectroscopy is another useful probe to diagnose
the number of layers and disorder in graphene [8589]. This
technique has also been commonly used to investigate the
quality of the electrochemically produced GNs in several
electrolytes [21,51]. The Raman spectra presented in Fig. 8,
obtained from EMIM BF4/acetonitrile electrosynthesis, display the well-known graphitic G peak at 1581 cm 1 (from
bond stretching of sp2 pairs in rings and chains), and a D
band at 1335 cm 1 (corresponding to the breathing modes
of sp2 atoms in rings) [21,90]. According to Ferrari et al.
[86], the evolution of the 2D peak (second order of D peak)
is a clear indication of structural transformation from
graphite to graphene heterostructures after electro-exfoliation. The sonication impact is also noticeable by increasing
the G/D peak ratios, which represent lower disorders therefore better graphene quality [91]. Importantly, G/D peak
intensity ratios represent the disorder in graphene in the
widest possible meaning [86,92]. In fact, there is a certain
chance for the incomplete electro-exfoliation or aftermath
agglomeration of the products which induces the disorder
effect. NMP is considered among the most promising candidates for the solvent-assisted graphite exfoliation [22,93],
and its effectiveness was evident in improving the overall
quality of our products. Brief sonication can also help to
more rigorously remove any physically adsorbed IL remnant/contamination on the surface of graphene which can
be another contribution to the quality enhancement. Moreover, these observations highlight the importance of implementing a systematic approach for isolating the effect of
all the processing and treatments methods performed on
the GNs in the course of synthesis. Similar trends were
observed for the exfoliation products synthesized with the
other investigated IL structures in this work (Fig. 2).
Lastly, X-ray photoelectron spectroscopy (XPS) analysis revealed nitrogen incorporation into the exfoliation products
via NHCs parasitic adsorption on the anode during electroexfoliation in EMIM BF4 electrolytes (Fig. 9). The presence of
the imidazolium moiety as well as the BF4 counter-ion is
inferable considering the XPS survey scan presented in
Fig. 9. A well-defined peak at 400.2 eV can be assigned to the

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(a)

(b)

(c)

(d)

(e)

(f)

Fig. 7 TEM and SEM images showing the variety of products generated by electrochemical exfoliation of iso-molded graphite
in EMIM BF4/acetonitrile electrolyte at 7 V and 293 K: (ad) crumpled/folded sheets, (e) semi-transparent carbonaceous
particles, and (f) rolled sheets.

N 1s of the imidazolium ring [54] (Fig. 9). The presence of B 1s

peak at 193.2 eV and F 1s at 686.6 eV represent the fingerprint
of BF4 anion remnants on the exfoliated flakes (<2%). It is
noteworthy that graphene has a high uptake for various gases
and airborne hydrocarbons therefore sensitive to such attachments [9497]. This poses serious uncertainties on the narrow
scan analysis of carbon and oxygen peaks so we avoid further
commenting on such areas in contrast with previous literature [50,54].

Graphene functionalization by imidazolium heterocycles

has been perceived as the main promoter for the rapid
dispersion of the GNs in NMP (1 mg ml 1) [53]. Such
concentrations are also readily obtainable via direct
liquid-phase exfoliation of graphite in NMP without any
functionalization, but requires much longer sonication times
(>8 h) [98,99]. Furthermore, the resulting suspensions
produced in this work remain stable after centrifugation and
sedimentation over a period of few months. We believe that,

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7 1 ( 2 0 1 4 ) 5 8 6 9

carbon types including amorphous. Additionally, we did not

capture any notable amorphous particle in our imaging experiments either.

4.

Fig. 8 Changes in the Raman spectra from graphite rod to

the final sonicated product obtained by electro-exfoliation in
EMIM BF4/acetonitrile at 7 V and 293 K after 4 h. (A color
version of this figure can be viewed online.)

Fig. 9 XPS data for the exfoliation products obtained from

EMIM BF4/acetonitrile electrolyte at 7 V and 293 K after 4 h:
survey scan, and N 1s narrow scan.

Summary and conclusions

We investigated the room temperature electrochemical exfoliation of iso-molded graphite anodes in a novel electrolyte
composed of IL and acetonitrile (1:50 vol. IL/solvent ratios)
using four different IL structures. Previous research was
focused only on IL/water mixtures with much higher IL
content (e.g. up to 1:0.1 IL/water vol. ratios). Our approach
provides three main advantages: cost efficiency due to low IL
content, extended electrochemical stability in the nonaqueous electrolytes, and much higher exfoliation yields
caused by the effective anionic intercalation within the
graphitic layers. Thus, up to 86% exfoliation yield was
achieved in 4 h using BMPyrr BTA/acetonitrile (1:50 vol.
ratio). The anodic intercalation of the large oxygenated BTA
anions was observed to be promising in overcoming the strong
van der Waals cohesion among the graphitic layers. The major
products of the graphite exfoliation, for all the four tested ILs,
were crumpled and folded graphene sheets. In addition, some
by-products such as carbonaceous particles and rolled sheets
were isolated but in much smaller quantities. Furthermore, we
demonstrated the complementary role of sonication after
electrosynthesis for improving the overall quality of the graphene-based products characterized by the Raman spectra.
Previous research had also placed a great deal of emphasis
on the electrolyte coloration during electrosynthesis as an
indicator of various graphite exfoliation stages and nanostructure formations. However, using control experiments
(i.e. replacing graphite anode by a platinum wire), we revealed
that the reactions of the IL moieties with the electrodes along
with their unusual fluorescence behavior are mainly responsible for this false presumption. The cathodic reduction of
the cationic moieties such as imidazolium rings generates
carbene species that are reactive with the graphite anode
and interfere with the anionic intercalation. On the other
hand, the electrochemical reactions involving the IL provide
the opportunity for in situ functionalization of the graphene
sheets via redox species produced during the electrosynthesis
process. The resulting functionalized GNs can be used for a
variety of applications including energy storage/generation,
environmental remediation, biomedical applications and so
forth. In any case, via facile post-treatment techniques, any
functional group can be removed from the products if not desired. Finally, the research presented here could pave the way
for future studies on ionic-liquid-assisted electrochemical
production of GNs on large scales.
R E F E R E N C E S

besides functionalization, the high surface area of the products

generated by electrochemical exfoliation (over 250 m2 g 1) is
another key factor for fast and stable dispersion formation. Another possible explanation for this observation might be the
presence of amorphous carbon structures. However, Raman
analysis from over five regions of each sample offered a consistent association with GNs characteristics rather than other

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