3+

Synthesis of green Fe /glucose/rGO electrode for supercapacitor application assisted

by chemical exfoliation process from burning coconut shell
Gilang B. A. Putra, Herdy Y. Pradana, Dimas E. T. Soenaryo, Malik A. Baqiya, and Darminto

Citation: AIP Conference Proceedings 1945, 020040 (2018); doi: 10.1063/1.5030262

View online: https://doi.org/10.1063/1.5030262
View Table of Contents: http://aip.scitation.org/toc/apc/1945/1
Published by the American Institute of Physics

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 Synthesis of Green Fe3+/Glucose/rGO Electrode for
Supercapacitor Application Assisted by Chemical
Exfoliation Process from Burning Coconut Shell
Gilang B.A Putra1, Herdy Y. Pradana2, Dimas E.T Soenaryo3, Malik A. Baqiya4,
Darminto5
Department of Physics, Faculty of Mathematics and Natural Sciences,
Institut Teknologi Sepuluh Nopember, Campus ITS Sukolilo, Surabaya 60111, Indonesia
Tel: (031)5994251 Ext 1224. Fax: (031) 5923411
1
E-mail: gilang.baswara.ap@gmail.com
2
E-mail: herdyyudhapradana94@gmail.com
3
E-mail: erikdimas13@gmail.com
4
E-mail: malikab@physics.its.ac.id
5
E-mail: darminto@physics.its.ac.id

Abstract. For the goal of large, environmental - friendly, renewable, and inexpensive energy storage, the development of
supercapacitor electrodes is needed, by anchoring transition metal oxide (Fe3+ ion) as pseudo capacitor electrode material
with reduced graphene oxide (rGO) from an old coconut shell as electrochemical double layer capacitor (EDLC). This
porous electrode composite is prepared by sonication and chemical exfoliation assisted by acid. Synthesis of
supercapacitor is also added by glucose, which acts as a spacer between layers of rGO to increase the capacitance, also as
binder between the materials used. Combining Fe3+ with old coconut shell rGO give high specific capacitance of up to 99
F/g at a potential window of -1 V to 1 V. The Fe3+/glucose/rGO electrode has thickness of up to 57 nm (from PSA result)
and give a uniform distribution from EDX mapping with disperse Fe domains and not bonding with rGO.

Keywords: Chemical Exfoliation, Electrochemical Double Layer Capacitor, Old Coconut Shell, Reduce Graphene Oxide

INTRODUCTION
With the rapidly growing technology nowadays, there has been an ever-increasing demand for energy storage
devices development. There are several types of energy storage devices, but supercapacitor is the most promising
ones. It has high energy density, long cycle-life, reversible, and fast charging. Supercapacitor is believed to be an
effective energy storage device because of the small dimension, using non-faraday reaction, and lightweight. It is
convenient with the ragone plot diagram which places the supercapacitor in the most favorable area, highest energy
capacity and medium discharging time (not too fast or slow) [1].
There are two types of supercapacitor, electrochemical double layer capacitor (EDLC) and pseudo capacitor.
EDLC generally use polymorph carbon just like graphene as material for the electrode, and pseudo capacitor use
metal oxide. EDLC has long cycle-life but low capacity and vice versa, pseudo capacitor has high capacity but short
cycle-life[2], [3]. There is some research that had been held to solve this problem by combining these two types of
supercapacitor, and it is proven to be worked [4]–[8].
Graphene has been an interesting research topic for this decade because of its excellence on electronic
properties[9], thermal conductivities[10], mechanical properties[11] and high surface area[12]. Reduced graphene
oxide (rGO) is more preferred to be used than graphene because of its practical production than graphene. Usually
rGO is produced by Hummer’s method from graphite[13].Further, rGO can also be produced by carbonizing old
coconut shell. It has main molecule bonding C=C and C-C. It is also having a lot of other atomic bonds, such C-H,
C-O, C=O, and O-H. Raman spectroscopy result shows that this compound has peaks at 1300 cm-1 and 1590 cm-1
with ID/IG ratio about 2.5 and XRD pattern peaks at 25˚ and 40˚ that indicating rGO phase [14]–[17].
In general, rGO will be treated mechanically or chemically in order to obtain thinner layers. The most effective
technique in exfoliating rGO layers is to use acidic solution. RGO is mixed using strong acids such as HCl or H 2SO4
to allow the strong acid to insert between the rGO layers. Then the solution is heated at 750oC. The Van der Walls
bond between layers will weaken and be easily detached. So, with this technique, rGO from old coconut shell will
have thinner layer and get high surface area [12].

Proceedings of the 3rd International Conference on Materials and Metallurgical Engineering and Technology (ICOMMET 2017)
AIP Conf. Proc. 1945, 020040-1–020040-7; https://doi.org/10.1063/1.5030262
Published by AIP Publishing. 978-0-7354-1640-6/$30.00

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 Fe3O4 is one of the metal oxide transition material that can be used as electrode material for pseudo capacitor.
This material is more environmentally friendly and more likely to find than the other metal oxide material[18]. It has
high pseudo capacitor capacitance, about 551 F/g. so it is favorable to use Fe3O4 as material for pseudo capacitor
electrode[7].
Mixing glucose with electrode material can enhance its capacitance. Glucose can act as binder for composite
electrode material and as spacer in rGO interlayer. This will increase the surface area of the electrode. With
increasing surface area, the capacitance will also increase[19]. The addition of glucose can increase the capacitance
value up to 200 F / g compared to the rGO electrode which is only 107 F/g only
In this research, we try to combine Fe3O4 as pseudo capacitor electrode material, rGO form old coconut shell as
EDLC electrode material, and glucose as spacer to increase the surface area of the electrode. The process also
assisted with HCl for mechanical-chemical exfoliation for rGO layer. We hope mixed rGO/glucose/Fe3O4 as
electrode will create an environmentally friendly, using abundance material, high capacitance and long cycle-life
supercapacitor.

METHODOLOGY
Synthesis of Sample
Sample preparation was done by remove the coconut fiber from the shell. Then the shell is burned in the open air
until it becomes charcoal and mashed by mortar until 200 mesh. Furthermore, it was heated using furnace at
temperature 400oC for 3 hours to evaporate water excess. This produces rGO powder which basic material for
electrode.
The rGO powder from burning process of old coconut shell was then mixed with another material. Typically, 1 g
glucose (dextrose monohydrate) was slowly added into in a 100 mL rGO suspension (1.2 mg/mL of HCl 1M),
followed by the addition of 0.75 g ‡Žଷ ή ͸ଶ ܱ. The suspension was then stirred at 75oC for 20 hours. With
intensive ultrasonication using ultrasonic cleaner (500 watts) for 6 hours, suspension was then dried until forming
slurry. Finally, the resulting stable black slurry was then pressed into pellet and dried at 110oC overnight. This
process resulted in electrode of FG11 with ratio of rGO: HCl: glucose: FeCl3 = 1:1:1:1.
For comparison, the composition of FeCl3 was reduced to half with ratio rGO: HCl: glucose: FeCl3 = 2:2:2:1
(FG21 electrode). To analysis effect of chemical-mechanical exfoliation, K11 sample were prepared without glucose
and FeCl3 with ratio rGO: HCl = 1:1 and sample G11 with ratio rGO: HCl: Glucose = 1:1:1.

Electrode Preparation
Conventional three electrode configurations were used in specific capacitance measurement of samples. Sample
electrode served as working electrode, while a Pt wire and an Ag/AgCl electrode were used as the counter and a
reference electrode, respectively. The working electrode was prepared by coating pellet with silver paste.

Characterization
Powder X-ray diffraction (XRD) was performed in Philips X’Pert MPD (Multi-Purpose Diffractometer) with Cu-
Kα radiation (ߣ = 1.54060 nm) in the 2ߠ range from 5o to 50o. Images and composition were obtained digitally on
scanning electron microscope (SEM) and electron dispersive X-ray (EDX). Particle size and distribution were
measure by particle size analyzer (PSA) with dynamic light scattering (DLS) technique (Malvern Nanozizer).
Functional group also analyze with Fourier Transform Infra-Red (FTIR). Then electrochemical properties were
carried out with Cyclic Voltammetry (CV).

RESULT AND DISCUSSION

Phase, structure, composition, and morphology
This research uses base material from old coconut shell that is basically a bio-waste. The combustion process of
coconut shell is a process of carbonization with the aim of generating rGO phase that can be develop
This produced a diffraction pattern seen in Figure 1 showing the rGO of the old coconut shell in this study, compared
to that by Nugraheni [1] (Figure 1(b)), as well as the rGO and GO prepared by standard method [2] (Figure 1(c) and

020040-2
1(d)). There are two areas that resemble the wide peaks at an angle of 2θ at 24° and 44°. The appearance of two
peaks from diffraction pattern illustrates that rGO have been formed. This corresponds to the matching with
qualitative method to diffraction data from [20] which produces rGO of graphite using Hummer method also has 2
specific peaks at diffraction angles 25° and 44° (Figure 1(c)).

FIGURE 1. Comparison of diffraction pattern from (a) sample, (b) rGO from old coconut shell, (c) rGO from graphite, and
(d) GO

Figure 2 shows the exfoliation process using HCl and accompanied by mechanical treatment process. The process
is expected to reduce the particle size and thickness of the rGO layers, in orde to have higher surface area and
therefore higher capacitance. Adding acid to the old coconut shell rGO powder is intended to penetrate between the
layers of rGO. Therefore, when suspension heated, the distance between layers of rGO can expand and break the
existing weak bonds that produce a thinner layer of rGO. Mechanical treatment with sonication techniques is also
expected to help the exfoliation process by releasing weak bonds between layers. In addition, the addition of glucose
that has a short enough carbon chain will act as an electrode binder and inserted between rGO layers to avoid
agglomeration as spacer. Agglomeration of rGO coatings is unfavorable in electronic terms, as it creates a closed
cavity that cannot be penetrated by electrolyte ions and reduces the effective surface area of the electrode. The third
ingredient added in the form of FeCl3 with Fe3+ ion is expected to be anchored on rGO surface and increase the
capacitance through the oxidation-reduction reaction in the charges-discharges process in super-capacitor electrodes.

FIGURE 2. Scheme of exfoliation process of old coconut shell rGO powder

The PSA result shows progress in reducing the size of the electrode material. The rGO powders without
mechanical-chemical exfoliation process has size up to thousands of nanometers (black line in Figure 3). After the
chemical and mechanical exfoliation process, electrode has particles below 500 nm. Each variation of electrode
produces 2 peaks with different intensities. Interpretation of PSA measurement results can be assumed that the
electrode particle has flakes shape. For example, in Figure 3 for FG21 variation there are two peaks. The first peak
has a particle size of 70 nm with an intensity of 4.4% and the second peak has a size of 400 nm with an intensity of
29.3%. This indicates that the smaller peak is the thickness of the rGO powder. This is due to the probability of
exposure flakes diameter is greater than flakes thickness. So, it can be assumed that the FG11 sample has a thickness
of 70 nm and the upper surface diameter of 700 nm. However, this needs to be proven through surface morphology
using SEM, exhibiting cross-sectional area of G11 and FG21 electrodes. It shows rough surfaces on both pieces of
the electrode. It is useful in increasing the surface area of the electrode so more ions able to be attached. While in
general, both samples are flake-like. In Figure 4(b), it exhibits the approximate thickness of the plate is 0.5

020040-3
micrometers or 500 nm. This supports the previous PSA measurements that the probability of its thickness varies
between 70 nm to 700 nm. But most of the electrode material has a flakes shape. The resulting results are close to the
rGO form in general, so the exfoliation process has been successfully performed.

FIGURE 3. Particle structure comparison between each variation of sample from Particle Size Analyzer result measurement
While the results of the elemental mapping using EDX (Figure 4(c) and 4(d)) shows the distribution and
composition of elements being present in the electrode. In general, both samples contain carbon (C) and oxygen (O)
that have been spread evenly. There is also an impurity element that plays a small role in its application like Al or Cl.
The FG21 electrode shows also a dispersed uniformly iron (Fe) element by the electrode. In addition, in EDX
mapping, tosca and red colored area does not occur overlapping, so it shows that Fe does not bind to the rGO. This is
corresponding with the original goal to simply anchored Fe to the rGO layer. This is supported by FTIR tests (Figure
5(b)). In the sample, there are only C-C functional bonds (3192.2 cm-1), C = C (1614.61 cm-1), and C-O (1012.19 cm-
1
) which is the main group of rGO samples. The Fe-O group (452.02 cm-1) indicates that Fe only binds to oxygen and
produces metal oxide.

(a) (b)

(c) (d)
FIGURE 4. SEM observations of (a) G11 sample, (b) FG21 sample, and EDX mapping for (c) G11 sample, (d) FG21 sample

020040-4
 (b)
(a)
FIGURE 5. Tranmitance result of FTIR from sample (a) G11 and (b) FG21

Electrochemical Properties
In order to explore the electrochemical properties of the rGO/glucose/Fe3+ electrode in a supercapacitor, an
electrochemical test with method of cyclic voltammetry (CV) was used. We investigated the supercapacitance
properties with KOH 6M electrolyte solution using with conventional configuration of three electrodes. The
electrodes used were working electrodes (samples), reference electrodes (Ag), and counter electrodes (Pt) with a
current injection of 1 A/g and a scan rate of 50 mV/s. The potential was given by see-saw model potential output.
Figure 6 shows the current-to-voltage response curve applied to electrodes in the range of -1 V to 1 V. The resulting
CVs curve forms quasi-rectangular shapes with different area of each sample variation. The largest and most closely
square shaped area is variation of the FG21 sample whose Fe concentration is smaller than that of other constituents.
Other curves produce different responses, this corresponds to ion transport and the conductivity of the electrons in
the sample. In addition, the addition of Fe3+ ions can also greatly affect ion transport, because of the additional ions
involved during the charge and discharge process. The CVs curve of a K11 sample consisting only of rGO that have
passed through the exfoliation process, has a low anodic and cathodic peak, which is generated by non-faradaic
reactions so it is reasonable to have a small enough extent.

FIGURE 6. CV curves of electrode sample recorded in scan rate 50 mV/s and 6M KOH solution

020040-5
 The curve deviation from the normal line represents the pseudocapacitive response of the electrode. The farther
deviation from the normal line, the more pseudocapacitive events occur. That many can be caused by electrolytes
and electrode materials. The discharge process (positive voltage applied) and charge process (negative voltage
applied) occur symmetrically which indicates the electrochemical process that occurs reversible. The capacitance of
the electrodes can be estimated using the following equation:
௏మ
ͳ
‫ܥ‬ൌ න ‫ܫ‬ሺܸሻܸ݀ (1)
݉‫ݒ‬ሺܸଶ െ ܸଵሻ
௏భ

TABLE 1. Specific capacitance of electrode sample from CV measurement

Composition Ratio Specific Capacitance Energy Density
Sample
(rGO:HCl:Glucose:FeCl3) (F/g) (Watt/g)
K11 1:1 20.8 0.282
G11 1:1:1 39.7 0.537
FG11 1:1:1:1 84.0 1.135
FG21 2:2:2:1 99.5 1.345

Which ݉ represents the mass of electrodes in grams, ‫ ݒ‬is the scan rate used, ܸଵ and ܸଶ are the top and bottom
potentials respectively. The result of estimation of specific capacitance value can be seen in Table 1.
In Table 1, there is an increase of capacitance value along with the addition of electrostatic material. The K11
electrode with only rGO material has a capacitance of only 20.8 F/g. But when given the addition of glucose that acts
as a spacer the capacitance increases almost twice as much as 39.7 F/g. This phenomenon is possible, because in
rGO electrode samples, the rGO layer still agglomerates and creates pores that cannot be passed by ion carriers. So,
the surface area is not effectively capture the ion. However, when given glucose that prevents the agglomeration of
the rGO layer, the ions can enter freely and attach to the rGO surface resulting in increased capacitance.
Along with the addition of Fe3+ ions with the same composition ratio, the capacitance increased again twice as much
as 84 F/g. This is also accompanied by the increasing symmetry of the CVs curve, which signifies a stable
electrochemical reaction and reversible. This increase in capacitance is due to the increase in load-carrying
concentration derived from the addition of Fe3+ ions. However, when the Fe3+ concentration on the electrode is
reduced, the capacitance is close to 100 F/g. This indicates too much Fe3+ also resulted in ineffective charging and
discharging process. So, the electrode obtained with the composition of rGO / Glucose / Fe3+ is most effective with a
composition ratio of 2: 2: 2: 1.
The estimated energy density of the rGO / glucose / Fe3+ electrode is 1.345 W/g. This estimate conforms to the
commercial supercapacitor characteristics that exist on the market. This estimate is based on the following equation:
ͳ
‫ ܧ‬ൌ Ǥ ‫ܥ‬Ǥ ሺȁܸଶ െ ܸଵ ȁሻଶ (2)
ʹ
With the results described above, a supercapacitor electrode generated through this processes and materials has a
high capacitance up to 99.5 F / g

CONCLUSION
The chemical-mechanical exfoliation process, the addition of glucose as a spacer, and the addition of Fe 3+ to the
super-capacitor electrode have induced positive results in increasing the capacitance of rGO electrode prepared from
coconut shell up to 99.5 F/g. This can be a new hope alternative in the development of supercapacitors utilizing
environmental-friendly and abundant sources. However, the life cycle of supercapacitors using Fe3+/glucose /rGO
based upon this coconut shell should further be investigated.

ACKNOWLEDGMENTS
This work is partly supported by “Hibah Kompetensi” research grant, DRPM, Ministry of Research, Technology
and Higher Education, Republic of Indonesia, 2017.

020040-6
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