Synthesis and Characterization of Graphene From Coconut Fiber (Cocos Nucifera) as Anode Materials For Li-Ion Battery

(Indra Gunawan)

Akreditation No : 21/E/KPT/2018
Date 9 July 2018
ISSN 1411-1098
E-ISSN 2614-087X

SYNTHESIS AND CHARACTERIZATION OF GRAPHENE

FROM COCONUT FIBER (COCOS NUCIFERA) AS ANODE
MATERIALS FOR Li-ION BATTERY

Indra Gunawan1, Wagiyo H2, Bambang Sugeng3 and Sudaryanto4

Pusat Sains dan Teknologi Bahan Maju (PSTBM) - BATAN
Kawasan Puspiptek, Serpong 15314, Tangerang Selatan
E-mail: irgun.ig@gmail.com

Received: 14 Desember 2018 Revised: 28 February 2019 Accepted: 6 March 2019

ABSTRACT
SYNTHESIS AND CHARACTERIZATION OF GRAPHENE FROM COCONUT FIBER
(COCOS NUCIFERA) AS ANODA MATERIAL FOR LI-ION BATTERIES. Synthesis of graphene from
coconut fiber conducted in two stages. The first stage is heating the powder of coconut fiber that passes
325 meshes by hydrothermal method at 200 oC for 4 hours. Furthermore, the pyrolysis then treated at
temperature of 1000 °C for 2 hours. The grain size and surface morphology from graphene observed using SEM
in the 1000X magnification. From the SEM image of graphene, it shows the pattern of several thick layers build
mutual three-dimensional, forming a flake structure. Observations also show stacks of graphene structure with
more big flakes forming a thick pallet. Another characterization was performed by using X-ray diffractometer
(XRD), Raman Spectrometer and LCR meter. From XRD observation there is an amorphous pattern at the first
stage of synthesis, after pyrolysis at 1000 oC for 2 hour a peak near 2θ = 24o, 42o and 52o which corresponds
to crystal indexes (002), (400) and (511) became visible. The peak at around 1350 cm-1 in the Raman is the D
band. The D band is represented defects, like disruption in the sp2 bonding because of heptagon and pentagon
rings, vacancies, edge effect, and etc. DC conductivity or bulk electrical conductivity of about 4.6 x 10-3 Scm-1.

Key words : Hydrothermal, Pyrolysis, Coconut fiber, Anode, Battery, Li-ion

ABSTRAK
SINTESIS DAN KARAKTERISASI GRAPHENE DARI SERAT KELAPA (COCOS NUCIFERA)
SEBAGAI BAHAN ANODA UNTUK BATERAI LI-ION. Sintesis graphene dari serat kelapa dilakukan dalam
dua tahap. Tahap pertama pemanasan serbuk sabut kelapa yang melewati 325 mesh dengan metode hidrotermal
pada 200 oC selama 4 jam. Selanjutnya, pirolisis kemudian dirawat pada suhu 1000 °C selama 2 jam. Ukuran
butir dan morfologi permukaan dari graphene diamati menggunakan SEM dalam perbesaran 1000X. Dari citra
SEM graphene, itu menunjukkan pola beberapa lapisan tebal membangun saling tiga dimensi, membentuk
struktur serpihan. Pengamatan juga menunjukkan tumpukan struktur graphene dengan serpih lebih besar
membentuk palet tebal. Karakterisasi lain dilakukan dengan menggunakan X-ray diffractometer (XRD), Raman
Spectrometer dan LCR meter. Dari pengamatan XRD ada pola amorf pada tahap pertama sintesis, setelah
pirolisis pada 1000 oC selama 2 jam puncak dekat 2θ = 24o, 42o dan 52o yang sesuai dengan indeks kristal (002),
(400) dan (511) menjadi terlihat. Puncaknya sekitar 1350 cm-1 di Raman adalah D band. D band direpresentasikan
sebagai cacat, seperti gangguan pada ikatan sp2 karena cincin segi tujuh dan segi lima, kekosongan, efek tepi,
dan lain-lain. Konduktivitas DC atau konduktivitas listrik massal sekitar 4,6 x 10-3 Scm-1.

Kata kunci: Hidrotermal, Pirolisis, Sabut kelapa, Anoda, Baterai, Li-ion

INTRODUCTION
Although graphene structure has been known achieved in 2004 by Andre Geim and Konstantin
since the 1960s, it was not possible to isolate such a Novoselov, who used adhesive tape to peel thin layers
monolayer until a few years ago. The feat was first off a graphite crystal [1]. Since then, this new
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nanomaterial has been the object of a large interest due active materials, are the most common devices at present.
to its peculiar and intriguing properties. Large-scale Graphene, with extraordinary properties such as high
graphene sheet is applicable to electronic devices, surface area, ultrahigh electrical conductivity and
whereas small-scale graphene can be used for optical superior mechanical flexibility, has become one of the
applications such as the saturable absorbers and most appealing conductive carbon matrices for
intensity/phase modulators for lasers [2]. Graphene is a nanostructured hybrids as electrodes [10,11].
single atomic plane of graphite, which is sufficiently Its large surface to mass ratio (SSA) of graphene
isolated from its environment to be considered free- exceeding 2600 m2g-1, high electrical conductivity (σ),
standing. Atomic planes are of course familiar to high mechanical strength, with the added value of mass
everyone as constituents of bulk crystals but one-atom- production, is a promising material for electrodes in Li-
thick materials such as graphene remained unknown. ion batteries. While single layer graphene (SLG), grown
The basic reason for this is that nature strictly forbids via chemical vapor deposition (CVD), has a limited
the growth of low-dimensional (D) crystals. Crystal capability of up taking Li ions (5% surface coverage)
growth implies high temperatures (T) and, therefore, due to repulsion forces between Li+ at both sides of the
thermal fluctuations that are detrimental for the stability graphene layer, large efforts have been devoted to the
of macroscopic 1D and 2D objects. One can grow flat exploitation of chemically modified graphene (CMG) such
molecules and nm-sized crystallites, but as their lateral as graphene oxide (GO) and reduced GO (RGO), both at
size increases, the phonon density integrated over the the anode and cathode [12,13]. However, although
3D space available for thermal vibrations rapidly grows, CMG can be produced in large quantities, they suffer
diverging on a macroscopic scale. This forces 2D from limited σ and diffusion of Li ions. To date, the best
crystallites to morph into a variety of stable 3D anodes with CMG have reached specific capacity
structures. The impossibility to grow 2D crystals does of ~1200 mAhg-1 at 100 mAg-1 current rate in half cell
not actually mean that they cannot be made artificially. and ~100 mAhg -1 at 29 mAg -1 current rate when
With hindsight, this seems trivial. Indeed, one can grow assembled in full battery [14-16].
a monolayer inside or on top of another crystal (as an Numerous studies have been found in litterateurs
inherent part of a 3D system) and then remove the bulk to use graphene as filler in the LiFePO4 as cathode
at sufficiently low T such that thermal fluctuations are material to increase its conductivity. In this paper we
unable to break atomic bonds even in macroscopic 2D report graphene synthesis that can be made as anode
crystals and mold them into 3D shapes [3]. It has attracted materials for Li-ion battery system.
great interest because of its advantageous material
properties, including high charge mobility, transparency, EXPERIMENTAL METHODS
mechanical strength and flexibility. Low crystalline
quality graphene is already used for several applications, Materials
such as composite materials and electrodes for batteries.
An ideal graphene sheet consists entirely of sp 2- The experiment was carried out by using materials
hybridized carbon atoms [4,5]. of Coconut fiber ash, other materials and solvents were
There are four main methods to synthesize of analytical grade, commercially available and used
Graphene. First method is the chemical vapor deposition without further purification.
and epitaxial growth and second method is
micromechanical exfoliation of graphite, this is also Methodology
known as the “Scotch Tape method” or the peel off
method, third method is epitaxial growth on electrically Synthesis of graphene from coconut fibers was
insulating surfaces, fourth method is based on creation conducted in two stages. The first stage is the heating
of colloidal suspensions [6]. However, chemical of the powder of coconut fiber passes in 325 meshes at
reduction of graphite oxide colloidal suspensions has a temperature of 200 o C for 4 hours. Further, pyrolysis
been considered as an effective route to synthesize was carried out at 1000 ° C for 2 hours with a nitrogen
graphene sheets due to its simplicity, reliability, ability atmosphere. Grain size and surface morphology of
for large-scale production and exceptionally low graphene observed using SEM with 1000X magnification.
price [7,8]. The crystal structure of graphene characterized by means
There is increasing strong interest in new energy of X-ray diffraction. The presence of graphene was
storage technologies to meet the future challenges of investigated using Raman Spectrometer. The
high-efficiency energy storage systems. Among the conductivity of graphene measured using LCR meter.
energy storage systems, electrochemical capacitors
(ECs) and lithium-ion batteries (LIBs) are currently RESULT AND DISCUSSION
considered to be the most promising energy storage
devices [9]. Of many different kinds of ECs, electric Graphene, a two-dimensional honeycomb
double-layer capacitors (EDLCs) using carbon-based lattice formed by a flat monolayer of hexagonally arrayed

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Synthesis and Characterization of Graphene From Coconut Fiber (Cocos Nucifera) as Anode Materials For Li-Ion Battery
(Indra Gunawan)

sp2-bonded carbon atoms, is the basal building block in sheets is a crucial property for constructing the 3D
all graphitic materials [17]. A scanning electron macrostructures.
microscope (SEM) image of resulting product of the first In Figure 2 there is an amorphous pattern at the
stage synthesis shows flakes like structures in Figure 1. first stage of synthesis, after pyrolysis at 1000o C for
2 hour a peak near 2θ = 24o, 42o and 52o which corresponds
to crystal indexes (002), (400) and (511) became visible.
This indicates the presence of oxygen functionalities.
According to the XRD patterns, mainly hexagonal
structure (2H) existed in graphite with a little
rhombohedral structure (3R) and did not change after
expansion. At the base of XRD analysis the 002 distance
was enlarged slightly due to intercalate reaction but still
kept the planar stacking structure. The pattern of the
sample contains very broad reflections at 24°
(corresponding to d spacings of 0.37), indicating
restacking to form an ordered graphite-like material.
These results suggest the existence of π-π stacking
between graphene sheets and also the presence of
residual oxygenated functional groups on reduced GO
sheets [18].

Figure 1. The morphologies of resulting product of the

first stage graphene synthesis (a) and second stage
graphene synthesis (b) investigated using SEM in the
magnification of 1000X.

The SEM images displays a flakes as the materials

was well-exfoliated (Figure 1). The majority of the flakes
were only a few layers thick and several tens of
micrometers in diameter. Figure 1(a) shows an individual
flake, elongated in the C axis which is 20 µm in diameter. Figure 2. XRD pattern from graphene result of synthesis
After further treatment graphite flakes were became route.
worm-like and twisted (Figure 1b), but also formed
lot of porous structure. The largest flake in Figure 1(b) Raman spectroscopy is a powerful non
is 60 µm in diameter. The appearance of bright destructive tool to characterize carbon materials,
edges and smooth stages across the area arises particularly for distinguishing ordered and disordered
from the presence of oxygenated functional groups [1]. crystal structures of carbon. The oxidation leads to a
The SEM image shows the pattern of several thick huge reduction in the size of graphite nanosheets in GO,
layers build mutual three-dimensional, form a flake compared to the size of the na- tural graphite flakes [1].
structure. As the preparation of graphene involves hydrothermal
Observations also showing stacks of graphene reactions in a solution, it is very likely some redox active
structure with more big flakes forming a thick pallet. Also, sites or defects are activated and remained on it, where
its layers are transparent and very thin. It could be the sharp Raman disorder-induced phonon mode
confirmed that mild oxidants and a hydrothermal (D-band), in Fig. 3 is perhaps the good indication for the
treatment contributed to the expansion of the graphite presence of defects. Raman spectroscopy was employed
flakes and helped to peel them into the thin graphene- to analyze the structural changes during chemical
like nanosheets. The SEM images of the sample display processing from graphene oxide to graphene. After
a wrinkled paper-like structure of the ultrathin graphene chemical reduction of graphene oxide, the conjugated
sheets and stacking of sheets. The partial overlapping graphene network (sp2 carbon) will be reestablished [1].
or coalescing of flexible graphene sheets resulted in the The D band which has been associated with
formation of physical cross-linking sites of the framework defects in graphene is rather uniform, except for regions
of the graphene. Thus, the inherent flexibility of graphene where wrinkles are present and close to few-layer

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600
500 Jurnal Sains Materi Indonesia Vol. 20, No. 3, April 2019, hal. 93-97
Raman Intensity
400

Figure 4. The log-log scale of conductivity measurement

300

on graphene.

This is mainly due to the recovery of conjugated system

200

from GO sheets upon hydrothermal reduction, as

confirmed by the X-ray diffraction (XRD) patterns. The
100

complex conductivity follows Jonscher’s power law and

is varied with angular frequency [20]:
0

500 1000 1500 2000 2500 3000 3500

Wave number cm-1 ................. (1)
Figure 3. Raman spectra from the marked spots with
corresponding the presence of graphene. where:
σdc = DC conductivity
regions. The G band is near the background level and A, = The AC conductivity parameter
the D band clearly show the presence of more than one n = Power law exponent
layer in the flakes. In the wrinkled regions, there are
The conductivity plots were fitted to Jonscher’s law
peak height variations in both the G and D bands, and
equation using a non-linear least squares fitting
there is a broadening of the D band. From the result, it
procedure to extract the conductivity parameters. Fitted
clearly seen at the Fig. 3 that the sample consists of two
values are A=10E-11.062 and n = 1.4555.
dominant peaks at 1350 cm-1 and 1590 cm-1. The peak at
around 1350 cm -1 is the D band. The D band is
represented defects, like disruption in the sp2 bonding CONCLUSION
because of heptagon and pentagon rings, vacancies, Synthesis of graphene from coconut fibers
edge effect, and etc. The defect also caused by wrinkle conducted in two stages produce large area graphene.
formation and the presence of functional groups [19]. This method was carried out with the conversion level
2D peaks didn’t appear in this work. Furthermore, Raman of graphite flakes to graphene and shows that graphene
spectroscopy was performed to indicate the structures is formed. XRD conform its graphene to hexagonal
of graphene by the resulting characteristic G and D structure. SEM images show an individual flake,
bands sensitive to defects and disorder, respectively. elongated in the C axis which is 20 µm in diameter. After
An analysis of the intensity showed that the area with further treatment graphite flakes were became worm-like
the lightest is more than 90 %, and all Raman spectra and twisted, but also formed lot of porous structure.
randomly collected from this area show monolayer The largest flake is 60 µm in diameter. The D band which
graphene. has been associated with defects in graphene is rather
The log-log scale of conductivity measurement uniform except for regions where wrinkles are present
on graphene is shown in Fig. 4. The electrical and close to few-layer regions. 2D peaks didn’t appear
conductivity of the electrolyte was calculated by in this work. Furthermore, Raman spectroscopy was
equation, σ = λ/(RbXA) where Rb is the bulk resistance performed to indicate the structures of graphene by the
from AC impedance, λ the film thickness and A the resulting characteristic G and D bands sensitive to
surface area of electrode. The DC phenomenon of this defects and disorder, respectively. The measurement of
conductivity found in low frequency to the high DC conductivity was 4.6 x 10-3 Scm-1.
frequency of this measurement. Meanwhile in highest
range frequency the conductivity followed AC
ACKNOWLEDGEMENTS
conductivity phenomenon. In addition to the excellent
apparent mechanical strength, the G is electrically We would like to thanks to Dr. Abu Khalid Rivai,
conductive with a DC conductivity or bulk electrical as Lead of BSBM and Prof. DR. Ridwan as Lead of
conductivity of about 4.6 x 10-3 Scm-1, which is also an PSTBM BATAN to support the research and writing of
attractive property for many practical applications [18]. this scientific paper.

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(Indra Gunawan)

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