Activated Carbons from Orange Peel Waste

as Supercapacitor Electrodes

Arenst Andreas Arie
1*,
Hans Kristianto
1
, Joong Kee Lee
2

1
Department of Chemical Engineering, Faculty of Industrial Technology,
Parahyangan Catholic University, Ciumbuleuit 94 Bandung 40141, Indonesia
2
Energy Storage Center, Korea Institute of Science and Technology, Hwarangno 14-gil 5,
Seongbuk-gu, Seoul 136-791, Korea
*Corresponding author. Email address:arenst@unpar.ac.id

In this work, activated carbon was prepared from Indonesian local
orange peel using ZnCl
2
activation method at various chemical
ratio. Carbonization was done for 1 h at 500
o
C. The structural and
morphological characteristics of orange peel based activated
carbons were investigated using scanning electron microscope
(SEM), Brunaeuer-Emmett-Teller surface analyzer. The highest
surface area was found about 1200 m
2
/gr, obtained from the mass
ratio of 1:2 (biomass : ZnCl
2
). Electrochemical measurement was
examined by half cells, using 1 M LiPF
6
in EC/EMC/DMC
solution (1:1:1 v/v) as electrolyte, and Li/Li
+
as reference
electrode. It was shown from cyclic voltammetry (CV) results
that activated carbon from orange peel demonstrated a stable
electrochemical characteristics, with specific capacitance of 56
F/g at scan rate of 1mVs
-1
at voltage window between 2.5 and 4
V.

Introduction

Recently, lithium ion capacitor has become a new promising energy storage device,
which can give higher power density than batteries, and higher energy density than
conventional electric double layer capacitor (EDLC) [1-4]. This superior performance is
due to the combined advantages of EDLC and lithium battery. Activated carbon was
usually synthesized from non renewable resources such as coal. However, in the past
decades, many efforts have been done for developing activated carbons from renewable,
cheap, abundant materials, such as peels, fruits stones, nut shells, etc [5-8].
In this research, Indonesia local orange peel (Citrus nobilis var microcarpa) was
utilized as precursors for activated carbons as electrodes in lithium ion capacitors.
Chemical activation was done by using ZnCl
2
as impregnant. The specific objective of
this work is to study effects of various chemical ratio on surface area and morphology of
activated carbon originated from orange peel. Furthermore, the electrochemical
characteristics of activated carbons as electrodes in Li-ion capacitors will be investigated
by typical cyclic voltammetry (CV) instruments.





10.1149/05331.0009ecst The Electrochemical Society
ECS Transactions, 53 (31) 9-13 (2013)
9 ecsdl.org/site/terms_use address. Redistribution subject to ECS license or copyright; see 161.122.73.161 Downloaded on 2013-10-15 to IP ecsdl.org/site/terms_use address. Redistribution subject to ECS license or copyright; see 161.122.73.161 Downloaded on 2013-10-15 to IP ecsdl.org/site/terms_use address. Redistribution subject to ECS license or copyright; see 161.122.73.161 Downloaded on 2013-10-15 to IP ecsdl.org/site/terms_use address. Redistribution subject to ECS license or copyright; see 161.122.73.161 Downloaded on 2013-10-15 to IP ecsdl.org/site/terms_use address. Redistribution subject to ECS license or copyright; see 161.122.73.161 Downloaded on 2013-10-15 to IP

Experimental

Orange peel was obtained from local market in Bandung, Indonesia. The orange peel was
repeatedly washed to remove dust and impurities, and then oven dried at 110
o
C for 24
hours. Dried orange peel was crushed to powder with particle size below 100 mesh. This
orange peel powder was used as activated carbon precursors. Chemical activation was
done by mixing 10 grams of orange peel with ZnCl
2
(Merck-p.a) at various mass ratio in
100 mL distilled water. These mixtures were shaken for 24 hours. The mixture then
centrifuged at 6.000 rpm for 15 minutes. The cake was then oven dried at 110
o
C for 24
hours. The dried cake was carbonized using electrical furnace at 500
o
C for 1 hour under
N
2
atmosphere. The activated carbon was washed using 0,5M HCl then repeatedly
washed using distilled water until neutral. The activated carbon was oven dried at 110
o
C
for 24 hours and stored in desiccators.
The working electrode was prepared by coating slurries containing activated carbon
(85%), carbon black (SuperP-10%), and polyvinylidene fluoride (PVdF-5%) dissolved in
n-methyl-2-pyrollidinone (NMP) on aluminum foil. After coating, the resulting
electrodes were cut into 2 2 cm square sheets, pressed, and dried in vacuum oven at
85
o
C for 12h. Lithium foil was used as counter electrode. Pouch type half cell was
assembled in a dry room (humidity lower than 0,3%) by sandwiching a polypropylene
membrane (Celgard 2400) between the two electrodes. 1M LiPF
6
in EC/EMC/DMC
solution (1:1:1 v/v) was used as electrolyte
BET surface area was analyzed using Micromeritics apparatus (ASAP 2010), and
SEM images obtained by using FE-SEM, S4100,HITACHI. Cyclic voltammetry (CV)
test was conducted using a Maccor automated battery tester (series 4000). Cell
capacitance from CV test [F/g] was calculated by the following equation:

C
CV
= (|I|.t)/(2.m. V) (1)

where (|I|.t) is the area of the current [A] against time [s] curve, m the mass of ative
material in the electrode [g], and V the potential window [V]


Results and discussions

Surface area and morphology of activated carbon. The mass ratios of orange peel and
ZnCl
2
used for chemical activation were 4:1, 2:1, 1:1, and 1:2. Fig. 1 shows the obtained
activated carbon at various chemical ratio. From Fig.1 it can be seen that at higher
chemical ratio used in activation, the obtained activated carbon became more porous. But
for ratio 1:1 and 1:2, the difference cannot be clearly seen just from SEM images. The
difference of pore characteristics can be seen quantitatively from Brunaeuer-Emmett-
Teller (BET) analysis, presented in Table 1. It can be clearly seen from Table 1 that
activated carbon pore characteristics are highly determined by its chemical ratio. At
higher chemical ratio, high surface area activated carbon was obtained. Optimum
micropore area was obtained at ratio 1:1, but the highest surface area is at ratio 1:2, with
large micropore narrow mesopore characteristics. Similar results were also obtained by
Lua and Yang (2005) for ativated carbon from pistachio nut shell. At low ratio, ZnCl
2
has
weak tar inhibition properties that influence volatile released that makes dominantly
microporous stuctures [5]. At higher ratio, there is micropores widening that makes a
ECS Transactions, 53 (31) 9-13 (2013)
10
dominant mesopores structure. This pore widening also gives better access for nitrogen
adsorption, thus giving a higher surface area. This result is in good agreement with other
researchers [5, 10, 11].

Figure 1. SEM images of activated carbon at ratio a. 4:1, b. 2:1, c. 1:1, d. 1:2

Table 1. Pore characteristics of activated carbon at various chemical ratio

Mass
ratio
S BET
[m
2
/g]
S Langmuir
[m
2
/g]
S Micropore
[m
2
/g]
Pore Volume
[cm
3
/gr]
Average Pore
Diameter []
4:1 4.3 5.9 4.4 0.002665 24.4
2:1 424 569.6 341.5653 0.212558 20
1:1 879 1185.9 636.7149 0.445293 20.2
1:2 1207 1627.9 365.5182 0.670697 22.2


The activated carbon with highest surface area was furthermore studied for its
electrochemical performances by CV test. CV tests was used to study the stability and
reversibility of activated carbon as cathode material. Fig.2 shows an ideal EDLC
characteristics with a symmetric rectangular shape indicating a good and stable
performances [12]. 63.83; 55.13; and 51.7 F/g capacitance was obtained at scan rate 0.1;
0.5; and 1 mV/s respectively.
Table 2 shows comparison of this work with other materials used as LICs cathode.
Activated carbon obtained from this work still had lower capacity than others work,
which carbon is modified. Further modification of obtained activated carbon should be
considered. Especially LICs overall performance is determined by the cathodes capacity
[13].
ECS Transactions, 53 (31) 9-13 (2013)
11


Figure 2. Cyclic voltammograms of activated carbon ratio 1:2

Table 2. Capacitance of other works on LICs cathode

Electrode type Measurement Capacitance Reference
Oxidized carbon
onion
3E, RE Li foil, 1M LiPF
6

(EC:EMC:DMC = 1:1:1), CV
1mV/s, 1.5-4.5 V
60 F/g [14]
Cu-doped activated
carbon
3E, RE Li metal, 1M LiPF
6

(EC:EMC:DMC = 1:1:1),
GCD 4A/g, 2-4 V
59.25 F/g [3]
Activated carbon from
orange peel
3E, RE Li metal, 1M LiPF
6

(EC:EMC:DMC = 1:1:1), CV
1mV/s, 2.5-4 V
51.7 F/g this work


Conclusions

Activated carbon prepared from Indonesia local orange peel was tested as LICs cathode.
Maximum surface area of activated carbon was obtained at 1:2 ratio, carbonized at 500
o
C
for 1hour. This activated carbon had micro-mesoporous characteristic with surface area
1200m
2
/gr. From CV test, it was shown that the activated carbon gave a good stable
electrochemical characteristics, with specific capacitance of 56 F/gr at scan rate of 1
mVs
-1
at voltage window between 2.5 and 4 V.


Acknowledgments

This work was financially supported by the Korea Institute of Science and Technology
(KIST) under the IRDA Alumnae Cooperation Project between KIST and UNPAR.

ECS Transactions, 53 (31) 9-13 (2013)
12

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