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Supercapacitor Electrodes from Activated Carbon Monoliths and Carbon

Nanotubes

Article in Journal of Physics Conference Series · April 2013

DOI: 10.1088/1742-6596/431/1/012015

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http://www.elsevier.com/locate/biombioe

Supercapacitors using binderless composite

monolith electrodes from carbon nanotubes and
pre-carbonized biomass residues

N.H. Basri a, M. Deraman a,*, S. Kanwal b, I.A. Talib a, J.G. Manjunatha a,

A.A. Aziz c, R. Farma a
a
School of Applied Physics, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi,
Selangor, Malaysia
b
H.E.J. Research Institute of Chemistry, International Centre for Chemical and Biological Sciences, University of
Karachi, Karachi 75270, Pakistan
c
Malaysian Palm Oil Board, P.O. Box 10620, 50720 Kuala Lumpur, Malaysia

article info abstract

Article history: Binderless composite monolith (BCM) electrodes prepared from carbon nanotubes (CNTs)
Received 11 April 2013 and self-adhesive carbon grains (SACGs) were used in a symmetrical supercapacitor. The
Received in revised form SACGs were prepared from fibers of oil palm empty fruit bunches (EFBs) from oil palm tree
22 August 2013 (Elaeis guineensis), Heliotropium dasycarpum (H. dasycarpum) and Guaiacum officinale (G. offici-
Accepted 26 August 2013 nale). For each biomass, the BCMs were prepared by the carbonization and activation of
Available online 17 September 2013 green monoliths (GMs) containing SACGs treated with KOH and a mixture of SACGs and
CNTs treated with KOH. Thermal decomposition behavior of all SACGs was found to be
Keywords: slightly different because of the difference in their compositions. In addition, BCMs from H.
Elaeis guineensis dasycarpum and G. officinale were found to have SiO2. The BET surface areas were 1656, 1031
Heliotropium dasycarpum and 532 m2 g
1 for the BCMs from EFB, H. dasycarpum and G. officinale, respectively, and
Guaiacum officinale these values decreased by 40, 50 and 31% upon CNTs addition. Consequently, the specific
Energy storage capacitance decreased from w124 to w104 and w49 F g
1 to w111, w87 and w31 F g
1,
Binderless composite electrodes respectively. However, addition of CNTs reduced the equivalent series resistance (ESR) by a
Porosity factor of 83.9 (EFB), 90.6 (H. dasycarpum) and 38.8 (G. officinale) %. It was also found that CNTs
addition contributed to improving the decay of Csp with increasing scan rate if the elec-
trode surface area was sufficiently high.
ª 2013 Elsevier Ltd. All rights reserved.

1. Introduction interface between the electrically charged surface of the

electrode and the ionic charges of the electrolyte solution [1,2].
Supercapacitors, ultracapacitors or electric double layer ca- The value of capacitance is generally proportional to the
pacitors (EDLCs), which consist of a pair of electrodes, an specific area of the electrodes [3], but there have been many
electrolyte and a pair of current collectors, store electrical cases where capacitance deviated from this proportionality
energy in an electrochemical double layer formed at the behavior [4]. Compared to conventional capacitors, the large

* Corresponding author.
E-mail addresses: [email protected], [email protected] (M. Deraman).
0961-9534/$ e see front matter ª 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.biombioe.2013.08.035
 b i o m a s s a n d b i o e n e r g y 5 9 ( 2 0 1 3 ) 3 7 0 e3 7 9 371

electrode surface area in supercapacitors can generate large hemicellulose and 25e35% lignin. In the dry form, the mean
energy storage capability or high capacitance values mass fraction percentages of chemical composition are as
(expressed in Farads) because large amounts of double layer follows: ash (6.3), oil (8.9), C (42.8), N2 (0.8), P2O5 (0.22), K2O (2.9),
are formed at the electrode-electrolyte interface and because MgO (0.3) and CaO (0.25).
the thickness of the double layers is very small (a few nano-
meter thickness depending on the diameter of the ion of the 2.1.2. Heliotropium dasycarpum (H. dasycarpum)
electrolyte solution used) [5]. H. dasycarpum is a heliotrope species that can be found
Activated carbon electrodes have been widely used as worldwide, mainly in tropical and subtropical regions,
electrode materials for supercapacitors because of their good including Kalat, Pakistan [28]. H. dasycarpum has been widely
physicochemical stability, high surface area, and well- used for traditional medicine and biomedical research
developed pore-size distribution, which can be adapted to because it contains a 1.92% mass fraction (dry weight basis) of
the size of the electrolyte ions [6,7]. Activated carbon produced medicinal bioactive compounds [23]. All H. dasycarpum plant
from biomass materials has been known to be extremely material obtained from Kalat, Pakistan was shade-dried and
porous because of interconnected cavities between pseudog- chopped, and its bioactive compound was extracted with
raphitic layers. These layers result in a high internal surface methanol [29]. This treated and shade dried H. dasycarpum
area and are of great interest for application as supercapacitor (1 kg) was supplied to our research group to be used as a
electrodes [8,9]. Therefore, biomass materials such as wheat precursor for the production of supercapacitor electrodes.
straw [10], rubber wood sawdust [11,12], waste tea leaves [13],
chicken feathers [14], seaweed carbon [15], oil palm empty 2.1.3. Guaiacum officinale (G. officinale)
fruit bunches (EFB) [16,17], sunflower seed shell [18], corn G. officinale, known to be a source of pure lignum vitae, is
grains [19], Neem dead leaves [20] and celtuce leaves [21] have commonly found in tropical areas, mainly in Central, North
been used as precursors to produce supercapacitor electrodes. and South America and including the Caribbean islands [24];
In the present study, fibers of EFB from oil palm tree (Elaeis additionally, it has been introduced and cultivated in Karachi,
guineensis) from Malaysia [22], biomass residuals from me- Pakistan [30]. G. officinale is a slow-growing, small to medium
dicinal extraction processes (three successive solvent extrac- sized tree that reaches 3e10 m in height [24]. Wood from G.
tions with methanol) of Pakistanis-flora (Heliotropium officinale is hard, heavy (oven dried density of 1050 kg m3),
dasycarpum) [23] and Jamaican-flower (Guaiacum officinale) [24] strong, long lasting, and it is known as an invaluable material
were pre-carbonized and processed to produce activated car- for construction and wooden household products [24]. Its
bon electrodes for supercapacitor applications. It is well extract has historically been used as a herbal medicine to cure
known that highly porous activated carbon electrodes have some diseases [24]. The bark of G. officinale plants cultivated on
very low electrical conductivity; to overcome this limitation, the premises of the University of Karachi was collected, air-
CNTs have been used as additives to reduce the electrical dried, chopped and extracted with methanol, which was
resistance of electrodes and improve the specific power of then concentrated under reduced pressure, to extract its
supercapacitors [16,25]. medicinal bioactive compounds [30]. For the present study,
The advantages of using biomass (or their derivatives) the resulting treated and shade dried bark was used as a
include their high availability, relatively low cost, sustainable precursor to produce supercapacitor electrodes.
and renewable sources and reduced environmental impact if
the biomass used is taken from waste generated by industrial
2.2. Electrode preparation and cell fabrication
activities. Biomass offers an alternative to the use of harmful
chemical precursors and thus reduces hazards during the
Based on the procedure previously developed for fibers of EFBs
synthesis and post-processing of electrode materials [26,27].
[16], H. dasycarpum and G. officinale residues were converted to
Moreover, the utilization of biomass materials for fabricating
SACGs by low temperature pre-carbonization (w280  C),
electrode materials to be used for energy storage devices will
grinding into a powder that passed through 300e500 mm hole
help to minimize the use of fossil materials (coal and
size filters, 18 h of ball-milling and sieving to obtain SACGs up
petroleum-based sources).
to 106 mm. Table 1 describes the SACGs prepared from EFB, H.

2. Materials and methods

Table 1 e Mixture composition and labels for all tested
2.1. Materials samples.
Biomass Mixture composition Green Binderless
2.1.1. EFBs from oil palm tree (Elaeis guineensis) (%) monolith composite
The fibers of EFBs were supplied by the Ecofibre Technology monolith
SACG KOH CNT
Sdn. Bhd. The properties of EFBs have been summarized
elsewhere [22]. EFBs consist of fibers or bundles of fibers that EFB 95 (SACG1) 5 0 GMK1 BCMK1
are stringy and flexible. The mass fraction of fresh EFBs 90 (SACG1) 5 5 GMT1 BCMT1
consist of 34% dry matter and 3% oil and 63% water and rep- H. Dasycarpum 95 (SACG2) 5 0 GMK2 BCMK2
90 (SACG2) 5 5 GMT2 BCMT2
resents approximately 20e22% of the weight of fresh fruit
G. Officinale 95 (SACG3) 5 0 GMK3 BCMK3
bunches. EFBs contain a lignocellulosic natural polymer ma-
90 (SACG3) 5 5 GMT3 BCMT3
terial with the mass fraction of 45e50% cellulose, 25e35%
372 b i o m a s s a n d b i o e n e r g y 5 9 ( 2 0 1 3 ) 3 7 0 e3 7 9

dasycarpum and G. officinale, labeled SACG1, SACG2 and SACG3, electrode can be calculated using equation (1) through equa-
respectively. The SACGs from EFB, H. dasycarpum and G. offi- tion (3) from the EIS, CV and GCD data [32]
cinale, and the mixtures of SACGs and CNTs were chemically
1
treated with KOH (Table 1). The CNTs used in this study were Csp ¼
(1)
pfZ00 m
50e100 nm in diameter and 5e10 mm in length, with a surface
area of approximately 40 m2 g
1 (Nano Amor Nanostructured
2i
& Amorphous Materials, Inc., Texas, USA, manufactured on Csp ¼ (2)
Sm
February 19th, 2009).
The green monoliths (GMs) were prepared by pressing

2i0 Dt
0.75 g of SACGs or mixtures of SACGs and CNTs in a 20 mm Csp ¼
(3)
m DV
diameter mold at 250 kg cm
2, and the respective labels are
shown in Table 1. Based on the previous multi-step heating where f is the lowest frequency, Z00 is the imaginary imped-
profile, the GMs were carbonized up to 800  C in a flow of ance at f, i is the electric current, S is the scan rate, DV is the
1.5 L min
1 N2 gas to produce the carbon monoliths [31]. The voltage different, Dt is the discharge period, i0 is the current
carbon monoliths were physically activated for 3 h at 800  C in density and m is the average mass of the electrodes.
a 1.0 L min
1 CO2 gas flow at a heating rate of 5  C min
1 to The specific capacitance (Csp) and its real (C0 ) and imagi-
produce BCMs, and their respective labels are shown in Table nary (C00 ) parts are widely evaluated as a function of the fre-
1. The BCMs were then polished to obtain a thickness of quency and can be calculated from the Nyquist plot produced
400 mm and extensively washed with distilled water until by the EIS measurements using equations (4)e(6).
reaching pH 7 before being used as electrodes in super- nn o1=2 o.
ðC00 Þ þ ðC0 Þ
2 2
capacitor cells. The mass (m), thickness (t) and diameter (d ) of Csp ¼ m (4)
the GMs and BCMs were measured, and their density was
calculated from these data. C0 ¼
Z00 ðuÞ =ujZðuÞj2 (5)
For investigation of the electrochemical properties of the
BCMs, symmetrical supercapacitor cells were fabricated using
C00 ¼
Z0 ðuÞ =ujZðuÞj2 (6)
the BCMs as their electrodes. The cell consisted of two BCM
0 00
electrodes, two stainless steel current collectors (thickness where Z (u) is the real impedance, Z (u) is the imaginary
50 mm) and an aqueous H2SO4 (1 mol L
1) electrolyte occupying impedance, C(u) ¼ C0 (u)
jC00 (u), and Z(u) ¼ 1/juC(u) [33].
space between the BCM electrodes separated by a Teflon The specific power and specific energy were calculated
spacer (thickness 100 mm). from the GCD data using equations (7) and (8), respectively

Vi
2.3. Physical characterization P¼ (7)
m

The thermal properties of SACGs were analyzed using Thermal

Vit
Gravimetry (TG) and Differential Thermal Gravimetry (DTG) in- E¼ (8)
m
struments (Mettler Toledo TGA/SDTS 851). The structure of
the BCMs was investigated using an X-ray diffractometer where V is the voltage, i is the current and t is the time.
(Bruker AXS D8) employing Ka Cu radiation of 1.5406  A and
scanning over the angular range 2q from 0 to 70 . The
morphological structures of the fractured BCMs were inves- 3. Results and discussion
tigated using a field emission scanning electron microscope
(FESEM) (Supra PV 55 model). Porosity of the BCMs was 3.1. Physical properties
investigated by conducting N2 adsorptionedesorption
isotherm measurements at 77 K using an accelerated surface The thermal properties of the SACG residues were investi-
area porosimeter system (ASAP 2020 Micromeretics). The gated over the temperature range of 20  Ce600  C, and the TG
porosity parameters, such as BET surface area (SBET), surface and DTG data are shown in Fig. 1. As seen, all of the SACGs
area of micropores (Smicro), surface area of mesopores (Smeso), exhibited a slight weight loss of approximately 10% with a
mesopore volume (Vmeso), micropore volume (Vmicro) and distinctly increasing rate of weight loss at temperatures of
average pore diameter (D), were obtained from the N2 30  Ce100  C, corresponding to the release of moisture and
adsorptionedesorption isotherm data using ASAP 2020 soft- water evaporation [34,35]. The decomposition of other vola-
ware and the standard formalism. tiles began at approximately 250  C, and the most weight lost
(approximately 50%) occurred between 250  C and 380  C. This
2.4. Electrochemical characterization thermal decomposition behavior is typical for most biomass
materials and is associated with the decomposition of hemi-
The fabricated symmetrical supercapacitor cells were char- celluloses, cellulose and lignin from the samples [36]. Specif-
acterized using electrochemical impedance spectroscopy ically, hemicelluloses begin to decompose at the lower end of
(EIS), cyclic voltammetry (CV) and galvanic charge-discharge this temperature range, followed by cellulose and lignin
(GCD) methods. The instruments used were a Solartron 1286 decomposition at slightly higher temperatures. For SACG1,
electrochemical interface and a Solartron 1255 HF frequency the maximum rate of weight lost was higher and occurred at a
response analyzer. The specific capacitance, Csp, of the lower temperature than SACG2 and SACG3, indicating that the
 b i o m a s s a n d b i o e n e r g y 5 9 ( 2 0 1 3 ) 3 7 0 e3 7 9 373

almost identical r values. However, the density of the BCMK3

(or BCMT3) increased by 36.57% (or 40.26%) from their
respective GMs, whereas the BCMK1 (or BCMT1) and BCMK2
(or BCMT2) decreased by 1.74% (or 0.45%) and 11.81% (or
10.73%), respectively. A slight increase (3.69%) in the r value
due to CNTs was observed for precursor 3, while the r value
decreased by 1.29% and 1.08% for precursors 1 and 2, respec-
tively, due to CNTs. The change in r is different between the
electrodes (with or without CNTs) from precursor 3 and the
electrodes (with or without CNTs) from precursor 1 and pre-
cursor 2. This result is because precursor 3 has a different
morphology and a higher degree of molecular cross-linking
compared to the other precursors. The density, hardness
and porosity of the carbonized products are influenced by
these properties because the mechanisms of releasing non-
Fig. 1 e TG and DTG curves of self-adhesive carbon grains carbon substances from the samples and the rearrangement
(SACGs) from biomass residues. of the carbon atoms to form turbostratic structures are
dependent on the precursors properties during carbonization
and activation. The morphology and molecular cross-linking
of precursor 3 suggest advantages over precursor 1 and pre-
SACGs from different types of biomass materials exhibited
cursor 2, as indicated by the higher density of GMs and BCMs.
different thermal decomposition behaviors. This behavior
Therefore, during the polishing of the BCMs, it was noticed
was evidence of the existence of slight variations in their
that BCM3 was tougher and harder to polish compared to
chemical structures and compositional ratios. Furthermore,
BCM1 and BCM2. This behavior is consistent with the density
the yields for SACG1, SACG2 and SACG3 at 600  C were 33.26%,
data presented in Table 2.
33.59% and 36.66%, respectively. For SACG3, the peak weight
Fig. 2 shows the X-ray diffractograms for all BCMs. The
loss rate was broader because it was a combination of two
structure of all BCMs was semicrystalline as evidently shown
peaks. The DTG results suggest that the peak weight loss rate
by the presence of two broad peaks due to (002) and (100)
for SACG3 (approximately 350  C) was broader because it was
diffraction planes at 2q approximately 25 and 41.6 , respec-
a combination of two peaks associated with the decomposi-
tively. These broad signals showed that the BCMs from all
tion of hemicellulose at approximately 310  C (lower left peak)
precursors have turbostratic structure; similar results were
and the 355  C (upper right peak). The absence of double peaks
reported previously for the BCMs from EFB [37]. The sharp
in the DTG results for SACG1 and SACG2 indicate that the
peak at 2q w 26.6 apparent in the diffractograms is attributed
hemicelluloses of the EFB and H. dasycarpum were completely
to the presence of crystalline SiO2 in the samples, which was
decomposed during the pre-carbonization process.
confirmed by the detection of Si using an energy dispersive x-
Table 2 shows the mass (m), diameter (d ), thickness (t) and
ray analysis (EDAX) measurement.
density (r) of the GMs and BCMs for all samples. The yields of
The micrographs of the BCMs fractured surfaces obtained
carbon electrodes prepared from GMs were estimated based
by FESEM at a magnification of 50k are shown in Fig. 3. The
on the data in Table 2. The yields of carbon electrodes pre-
obvious differences in microstructure between the BCMK and
pared from GMs without and with CNTs were 26e32% and
BCMT samples were clear. The presence of CNTs in the latter
35e40%, respectively. As seen in Table 2, the m, d and t values
samples in the micrographs appeared as cylindrical shapes
for all GMs samples were almost identical and gave rise to
similar to those reported by others [5,38]. CNTs seemed to

Table 2 e Mass (m), dimension (diameter, d and

thickness, t) and density (r) of the green monoliths (GMs)
and binderless carbon monoliths (BCMs).
Samples m (g) d (mm) t (mm) r (g cm
3)

GMK1 0.7381 2.3097 20.22 0.9957

GMK2 0.7381 2.3547 20.30 0.9692
GMK3 0.7323 2.1630 20.20 1.0566
BCMK1 0.2359 1.5317 14.13 0.9784
BCMK2 0.1943 1.5507 13.60 0.8547
BCMK3 0.2297 1.3052 12.53 1.4430
GMT1 0.7431 2.2490 20.14 1.0377
GMT2 0.7379 2.3103 20.19 0.9999
GMT3 0.7340 2.1210 20.13 1.0880
BCMT1 0.2946 1.6613 15.04 0.9914
BCMT2 0.2603 1.6830 14.79 0.8918
BCMT3 0.2712 1.3470 12.97 1.5260
Fig. 2 e X-ray diffractograms for all BCMs.
374 b i o m a s s a n d b i o e n e r g y 5 9 ( 2 0 1 3 ) 3 7 0 e3 7 9

Fig. 3 e FESEM micrographs for all BCMs.

uniformly disperse and occupy the pores of each material, 2 (50%), followed by sample 1 (40%) and sample 3 (31%). These
thus directly affecting the porosity of the samples. The pores values indicated a significant effect of CNTs on the pore
in these three materials were well distributed, but BCM3 characteristics of the electrodes, which could result from the
appeared to have less pores. occupation of CNT particles in some pores or the inhibition of
The porosity of the BCMs was investigated using N2 pore formation during carbonization and activation due to the
adsorptionedesorption isotherms (Fig. 4). Based on IUPAC presence of CNTs in GMs. Another notable trend in Table 3
data classification, the isotherm profiles for all BCMs exhibited was that the Smeso (or Vmeso) was higher than the Smicro (or
type IV patterns, similarly found in activated carbon from Vmicro), which was expected because the hysteresis loops in
rubber wood sawdust and seaweed carbons [11,15]. This type Fig. 4 were very pronounced. Furthermore, the D values were
represents the combination of microporous and mesoporous found to increase with the addition of CNTs. This increase
pore structures. The low P/Po region was associated with indicated that the CNTs caused pore widening during the
monolayer-multilayer adsorption on the mesopore walls, carbonization and activation processes.
while the high P/Po region was associated with limited uptake
and capillary condensation [39,40]. 3.2. Electrochemical properties
The SBET, Smeso, Smicro, Vmeso, Vmicro and D calculated from
the isotherms data are shown in Table 3. The results in this 3.2.1. Electrochemical impedance spectroscopy
table clearly show that the SBET was highest for BCMK1, fol- EIS curves (impedance data) over a frequency range of
lowed consecutively, which included micropores and meso- 10 mHze1 MHz for all BCMKs and BCMTs cells in Fig. 5 (a)
pores parameters, by a significant decrease for BCMK2 and exhibited typical frequency-dependent behavior of the
BCMK3. This trend was maintained by the BCMs with CNTs, Nyquist plot for carbon-based supercapacitors, depending on
but a significant decrease of surface area due to CNTs addition the frequency region. In the high frequency region, there was
was revealed by the data. The largest decrease was for sample a relatively small semicircle representing the dominant
resistive nature of the supercapacitor electrode/electrolyte/
current-collector system. In the middle frequency region,
there was a segment of a straight line with a slope of
approximately 45 , which represented the combination of
resistive and capacitive behaviors for the ions penetrating into

Table 3 e Porosity parameters obtained from N2

adsorptionedesorption isotherm data for all of the BCMs.
Sample SBET Smeso Smicro Vmeso Vmicro D (
A)
(m2 g
1) (m2 g
1) (m2 g
1) (cm3 g
1) (cm3 g
1)

BCMK1 1655.49 1010.94 644.54 0.3002 0.3645 22.04

BCMK2 1030.82 911.01 119.81 0.4757 0.0676 25.57
BCMK3 532.37 317.18 215.18 0.3297 0.1155 24.78
BCMT1 993.79 795.32 198.47 0.3265 0.1217 24.09
BCMT2 514.89 450.01 64.88 0.3124 0.0352 29.90
BCMT3 368.66 206.76 161.90 0.1191 0.9044 26.83
Fig. 4 e N2 adsorptionedesorption isotherms for all BCMs.
 b i o m a s s a n d b i o e n e r g y 5 9 ( 2 0 1 3 ) 3 7 0 e3 7 9 375

Fig. 5 e (a) Nyquist plots and (b) schematic Nyquist plots for all BCMs cells.

the electrode pores. In the low frequency region, there was a [10], 0.49 to 0.55 U for carbon from rubber wood sawdust [11],
segment of a sharply increasing straight line that represented and 0.74 to 0.78 U for carbon from waste tea leaves [13]. CNTs
the dominance of capacitive behavior from the formation of seemed to increase the Rs values, supporting their effect on
ionic and electronic charges in the electric double layer sys- the contact resistance between current collector and elec-
tem at the micropore surfaces. At this frequency, the ions trode. The Rp values appeared to vary with the electrode type
could more easily diffuse into the micropores [11]. and led to a notable difference in the ESR values of the cells.
The curve for each cell shown in Fig. 5 (a) had a similar The ability of CNTs to reduce the ESR values is clearly shown
general shape with a difference in their detail behavior due to in Table 4 for all types of electrodes. Comparison between the
the difference in the pore characteristics of their electrodes. ESR values of the BCMT cells showed that these ESR values
The detail differences were conveniently distinguished by decreased with decreasing surface area of their respective
analyzing these curves in terms of the parameters shown in electrodes. These behaviors have also been observed in recent
Fig. 5 (b). The parameters were Rs, the resistance of the elec- studies on supercapacitors using other carbon precursors,
trolyte and the contact resistance between the current col- which reported ESR values of 2.28 U, 0.97 U and 0.43U for
lector and electrode, Rp, the internal resistance of the surface areas of 2126, 1911 and 1839 m2 g
1, respectively [14].
electrode, the diameter of the semicircle, Rp
Rs, which is The reduction in the ESR values was not solely due to the
equal to the ESR (equivalent series resistance) value of the cell, change in surface area but also arose from the increase in
and fk, the knee frequency, which is an initiation point of the the electronic conductivity of the electrode upon addition of
dominant supercapacitive segment line in relation to its CNTs [41].
0
resistance, Rk ¼ Z k . Another trend that resulted from the addition of CNTs was
The values of Rs, Rp, ESR and fk for all the cells determined that for all three types of electrodes, the supercapacitive line
from the data in Fig. 5 (a) are listed in Table 4. The Rs values of the BCMT cell was positioned at a lower Z0 value than its
were small (less than 1 U) and typical for supercapacitors respective BCMK cell. A similar trend was observed in another
using H2SO4 as their electrolyte. A small difference in the Rs recent study [42]. Furthermore, CNTs also increased the Z00
values was due to the variation in the contact resistance be- value at the lowest frequency and hence decreased the Csp
tween the current collector and the electrode. These values of because it is inversely proportional to Z00 . The values of Csp
Rs were comparable with those reported in the literature, calculated from the EIS data using equation (1) are shown in
which ranged from 0.50 to 2.00 U for carbon from wheat straw Table 5. As seen, the Csp results for the BCMK cells showed a
decreasing trend and were consistent with the decreasing
surface area data shown in Table 3. The same trend was
observed for the BCMT cells, but with slightly lower values of
Table 4 e Rs, Rp, ESR and fk for all of the BCM cells. Csp. A similar reduction in the Csp values by CNTs was also
observed in other studies (i.e., 95 F g
1 and 90 F g
1 for
Cell Rs(U) Rp(U) ESR(U) fk(Hz)
cells using carbon electrodes without and with CNTs,
BCMK1 0.35 1.24 0.89 0.32 respectively) [43].
BCMK2 0.21 5.90 5.74 0.63 Fig. 5 (a) also shows that the supercapacitive lines for
BCMK3 0.36 1.27 0.93 e BCMK3 were significantly less vertical than type 1 and 2 cells.
BCMT1 0.39 0.54 0.14 0.25
This decrease in verticalness was a consequence of the
BCMT2 0.41 0.95 0.54 e
BCMT3 0.55 1.06 0.57 e
significantly lower surface area possessed by the electrodes in
this cell (Table 3). Addition of CNTs caused supercapacitive
376 b i o m a s s a n d b i o e n e r g y 5 9 ( 2 0 1 3 ) 3 7 0 e3 7 9

performed for supercapacitors using CNTs and carbon elec-

Table 5 e Specific capacitance (Csp), specific power (P),
specific energy (E ) and ratios of Smeso/Smicro for the tested trodes from CNTs and activated carbon materials [44].
cells. Fig. 6 (a), (b) and (c) shows the specific capacitance and real
(C0 ) and imaginary (C00 ) capacitance of the BCM cells calculated
Cell Csp(F g
1) E (Wh kg
1) P (W kg
1) Smeso/
(GCD) (GCD) Smicro using equations (4)e(6), respectively, as a function of fre-
EIS CV GCD quency. In Fig. 6 (a), the Csp strongly depended on the fre-
BCMK1 111 128.77 133 3.82 158 1.57 quency below 1 Hz, particularly for the BCMK cells, which
BCMK2 94 108.89 109 2.55 198 7.60 showed a higher Csp throughout the frequency region. A
BCMK3 23 98.80 25 0.43 134 1.47 similar frequency dependence was also exhibited by the C0
BCMT1 95 117.12 121 3.54 160 4.00 and C00 curves in Fig. 6 (b) and (c). For the C00 curve, there is a
BCMT2 73 102.57 85 2.53 173 6.94
peak frequency value ( fp). This frequency value is associated
BCMT3 15 68.22 10 0.17 133 1.28
with the relaxation time constant, so, which defines the
boundary between the regions of capacitive and resistive be-
haviors for a supercapacitor. It is well known that higher
cell performance to decrease because its slope decreased and power delivery corresponds to lower so values. Based on the fp
length increased (BCMT3 cell), which was consistent with a values in Fig. 6 (c), the value of so was estimated using the
further decrease in surface area of its electrodes (Table 3). It equation so ¼ 1/fp. The results obtained were 3.16, 1.58 and
will be seen in a later section that these inferior pore char- 3.98 s for the BCMK1, BCMK2 and BCMT1 cells, respectively.
acteristics of the type 3 electrodes affected the power and The so values for the other cells could not be calculated
energy performance of the cells. These results suggested that because the peaks fell below the detection limit of the
the addition of the CNTs would only be beneficial provided instrument.
that the surface area of the electrode was sufficient, as has
been observed elsewhere [32]. Contrary to the case of type 2 3.2.2. Cyclic voltammetry
electrodes which possessed surface area sufficiently higher; The cyclic voltammograms, recorded at a scan rate of 1 mV s
1
thus, addition of CNTs contributed significantly to reducing within the potential range of 0.1e1.0 V for all the investigated
the ESR from 5.74 to 0.54 U (Table 4). cells, are shown in Fig. 7. All voltammograms for cells 1 and 2
Ideal Warburg lines have a slope gradient of approximately had symmetrical rectangular shapes representing a common
45 [44]. Except for the BCMK1 cell, the slope and length of the supercapacitive characteristic for a carbon-based symmetri-
Warburg line for the other cells are shown in Fig. 5 (a). Inter- cal supercapacitor. These plots were evidence that these cells
estingly, their slope gradients were all lower than 45 . The had good reversibility and high EDLC stability during charge
length of the Warburg line seemed to change slightly with and discharge. This superior performance resulted from sig-
respect to electrode type and CNTs addition. It is well known nificant EDLC formation in the pores of the electrodes occu-
that a higher slope gradient and a shorter Warburg line are pied by 1 M H2SO4 electrolyte during the energy storage
associated with a better supercapacitive characteristic of a process [3,45]. Cells 1 and 2 also exhibited broader voltam-
cell. For electrode types 1 and 2, addition of CNTs increased mogram areas, indicating that they were superior to the other
the slope gradient by a factor of 27 and 9.3%, respectively. For types of cells. For cell 3, the voltammogram exhibited a rela-
electrodes of type 3, the Warburg line only appeared after the tively smaller window area, and the shape notably deviated
addition of CNTs. These results demonstrated that CNTs from the typical rectangular shape. Unlike cells 1 and 2, at
affected the mobility of electrolyte ions entering into pores of switching potentials (w0.1 and w1.0 V), the rapid current
electrodes in this intermediate frequency region and that the response of cell 3 to voltage diminished. This behavior indi-
extent of such an effect depended on the pore characteristic of cated an inferior performance for cell 3 due to the lack of fast
the carbon matrix. Examination of electrolyte ion mobility in ion transport in the EDLC system [38,45]. The Csp values
porous electrodes in the Warburg frequency region was calculated using equation (2) based on the data in Fig. 7 are

Fig. 6 e Evolution of (a) specific capacitance versus frequency, and (b) real and (c) imaginary capacitance for the BCM cells.
 b i o m a s s a n d b i o e n e r g y 5 9 ( 2 0 1 3 ) 3 7 0 e3 7 9 377

Fig. 7 e Cyclic voltammograms for the BCM cells. Fig. 9 e GCD curves at 10 mA cmL2 current density for all
BCM cells.

listed in Table 5 and clearly show that these results were

varied with the type of electrode used. The triangular area was
consistent with EIS and CV results.
broader for the BCMK1 cell and was decreased for the BCMK2
For electrode type 1, the addition of CNTs decreased Csp at a
and BCMK3 cells. Addition of CNTs further reduced the
lower scan rate and increased Csp at a higher scan rate (Fig. 8).
triangular area for all of the BCMT cells. A clear difference in
For electrode type 2, Csp improved significantly upon addition
the supercapacitive behavior between cells was observed in
of CNTs for all scan rate regions. In contrast to the two other
the Csp values calculated from the GCD curves in Fig. 9 using
electrodes, addition of CNTs to electrode type 3 enhanced the
equation (3). The specific Csp values are listed in Table 5, and
decay of Csp. At the scan rate of 100 mV s
1, the Csp for elec-
the trend of these values was in good agreement with the EIS
trodes type 1 and type 2 with CNTs remained higher, with only
and CV methods.
59% and 53% decay, respectively, compared to 76% and 93%
A slight voltage drop at the beginning of the discharge
decay without CNTs. Similar trends were observed in a study
curve appeared in all GCD curves in Fig. 9. This drop was
involving the addition of CNTs to activated electrodes pre-
associated with the ESR of the cells, which could be calculated
pared from fibers of EFB [46].
using ESR ¼ iRdrop/2I, where iRdrop is defined as the electrical
potential difference at the beginning of the discharge curves,
3.2.3. Galvanostatic chargeedischarge
and I is the discharge current [47]. The calculated ESR values
The GCD curves recorded at a current density of 0.1 mA cm
2
for the BCMK1, BCMK2 and BCMK3 cells were 1.68, 5.94 and
over a voltage range of 0.01e1.00 V for all the investigated cells
2.75 U, respectively. Addition of CNTs was found to decrease
are shown in Fig. 9. Each curve exhibited a similar isosceles
the ESR values of the cells to 0.99, 1.54 and 2.44 U for the
triangular shape with charge and discharge potentials varied
BCMT1, BCMT2 and BCMT3 cells, respectively. A similar
linearly with time. These shapes indicated that all cells
decrease in the ESR values by CNTs was observed in the study
exhibited supercapacitive behavior. However, the area under
of supercapacitors using porous carbon electrodes containing
the triangle, which represents the capacitive level of the cells,
CNTs (i.e., from 0.5 to 0.38 U in Ref. [43] and from 45 to 2.5 U in
Ref. [48]). The reduced ESR values could improve the power
performance of the cells because the power is inversely pro-
portional to ESR.

3.2.4. Ragone plots (specific power against specific energy)

The specific power (P) and specific energy (E ) of the cells,
calculated from the GCD discharge curves in Fig. 9 using
equations (7) and (8), respectively, are presented as Ragone
plots in Fig. 10. All PeE plots in this figure showed a typical
pattern of decrease in power as energy increased for carbon-
based supercapacitors. The BCMK3 cell demonstrated a
significantly poorer PeE relationship performance than the
other cells based on electrodes of type 1 and 2, i.e., its
maximum P and E were smaller. This poorer performance was
enhanced by the addition of CNTs (BCMT3 cell). For the BCMK2
cell, its maximum P value was the highest but decreased faster
within a lower and narrower E range compared to that of the
Fig. 8 e Cspversus scan rate for all BCM cells. BCMK1 cell. The effect of CNT addition was significantly
378 b i o m a s s a n d b i o e n e r g y 5 9 ( 2 0 1 3 ) 3 7 0 e3 7 9

addition of CNTs significantly affects the pore characteristic

and electrochemical behavior of the electrodes, (iii) the addi-
tion of CNTs is only beneficial if the electrode has significantly
higher surface area, (iv) the self-adhesive property of SACGs
prepared from biomass eliminates the need for a binder in
preparing electrodes in a monolithic form, (v) SACGs are
compatible with a high degree of reliability in mixing with
CNTs for the modification of electrode performance, and (vi)
the performances of electrodes from EFB and H. dasycarpum
are comparable to those of electrodes prepared from other
types of biomass precursors reported in the literature.

Acknowledgments

The authors are grateful to the UKM research grants UKM-

Fig. 10 e Specific power against specific energy, or Ragone
DLP-2012-022, UKM-DLP-2012-023, ERGS/1/2012/STG05/UKM/
plots, for all BCM cells.
01/2 and UKM-Industri-2013-026 for financial support of this
project. We would also like to acknowledge the Research
Institute of Chemistry, International Centre for Chemical and
greater for electrode type 2, particularly in the low E region. In Biological Sciences, University of Karachi, Karachi, Pakistan
contrast, electrode type 1 was significantly affected by CNT for the gift of materials, comments from Dr. Farrukh Mansoor,
addition only in the high E region. These features were and the instruments provided by CRIM, UKM.
strongly correlated with the pore characteristics of the elec-
trodes of the cells. To observe this correlation, Table 5 relates
the electrode pore characteristics (Smeso/Smicro) to their cor- references
responding PeE patterns for the present work and other data
reported in the literature. For comparison, Table 6 lists the
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