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Microwave synthesis of graphene/magnetite composite electrode material for symmetric supercapacitor with superior rate performance

Microwave synthesis of graphene/magnetite composite electrode material for symmetric supercapacitor with superior rate performance

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Published by karthik506
High performance symmetric supercapacitors.
High performance symmetric supercapacitors.

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Published by: karthik506 on Jan 02, 2013
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Microwave synthesis of graphene/magnetite composite electrode material forsymmetric supercapacitor with superior rate performance
{
Kaliyappan Karthikeyan,
a
Dharmalingam Kalpana,
*
b
Samuthirapandian Amaresh
a
and Yun Sung Lee
*
a
Received 6th August 2012, Accepted 25th September 2012
DOI: 10.1039/c2ra21715e
Pristine Fe
3
O
4
and Fe
3
O
4
 –graphene composites were synthesized by using a green and low cost urea-assisted microwave irradiation method and were utilized as electrode materials for symmetricsupercapacitor applications. The Fe
3
O
4
 –graphene symmetric cell exhibited a better electrochemicalperformance than that of the Fe
3
O
4
cell with enhanced rate performances. The Fe
3
O
4
 –graphenesymmetric cell delivered a stable discharge capacitance, energy and power densities of about 72 F g
2
1
,9 Wh kg
2
1
and 3000 W kg
2
1
, respectively at 3.75 A g
2
1
current density over 100 000 cycles between0–1 V. The impedance studies also suggested that the Fe
3
O
4
 –graphene symmetric cell showed lowerresistance and high conductivity due to the small particle size, large surface area and good interactionbetween Fe
3
O
4
particles and graphene layers.
Introduction
In recent years, research into alternative energy storage deviceshas drawn much attention due to the increasing environmentalconcerns and depletion of natural oil resources. Among theenergy storage devices, electrochemical supercapacitors (ECs)have attracted much interest due to their high power density,long cycle life, and higher energy density than conventionalcapacitors.
1
According to their charge storage mechanism, ECscan be classified as electrochemical double layer capacitors(EDLC) and pseudocapacitors. The former is based on thecharge separation at the electrode–electrolyte interface, whereasthe later is associated to the reversible Faradaic reaction of electro-active species such as surface functional group andtransition metal oxides at the electrode. Various carbonaceousmaterials with high surface area have been adopted as theelectrode materials for EDLCs.
2–4
The capacitance and energydensity of the pseudocapacitors are much larger when comparedto the EDLCs. The hybridization of two types of electrodes toform a new capacitor called a hybrid supercapacitor (HSC) is aunique approach that is used to enhance the electrochemicalproperties of single cell
5,6
. In this case, one of the electrodes is anenergy source electrode (battery-like electrodes) and the otherterminal contains a power source electrode (either an EDLC or apseudo capacitor electrode).The electrode materials for pseudocapacitors are either metaloxides
7
or conducting polymers
8
. Among the metal oxides, theoxides of Ru have been considered as promising electrodematerials for pseudo-capacitor applications because of theirhighest specific capacitance of 720 F g
2
1
.
9
However, theirprohibitive cost and toxic nature have motivated the search for acheaper material with an equivalent performance. Numeroustransition metal oxides such as MnO
2
, NiO, SnO
2
and Co
3
O
4
have been investigated and demonstrated as electrode materialsfor EC applications.
10–13
Of late, magnetite (Fe
3
O
4
) withdifferent valance states has become recognised as a promisingelectrode material for energy storage applications due to its lowcost, environmentally benign nature and natural abundance.
14,15
Nano-structured Fe
3
O
4
has already been used as a catalyst,
16
an anode for lithium batteries
17
and in magnetic devices.
18
Wu
et al.
was the first to report the capacitance nature of Fe
3
O
4
with
y
7 F g
2
1
in 1M Na
2
SO
4
electrolyte.
14
Chen
et al.
prepared anFe
3
O
4
thin film and demonstrated its electrochemical perfor-mance in 1 M Na
2
SO
3
solution.
15
Later, Wang
et al.
investigatedthe capacitance properties of magnetite in different aqueouselectrolytes.
19
However, the capacitances reported in the aboveliteratures are still very low, and hence, much effort is required toimprove electrochemical behavior. The preparation of advancednanocomposites has been extensively studied to improve thecapacitance behavior of Fe
3
O
4
, which could be achieved from itshigh stability and the improved conductive nature of thecomposites that enhances the pseudo-capacitive behavior of Fe
3
O
4
.
20–22
Among the nanocomposites, Fe
3
O
4
 –graphene exhib-ited an excellent capacitive performance, attributed to thesynergistic effects of the redox nature of metal oxides and thehigh electrical conductivity as well as the large surface area of graphene. There are few traces found relating to the utilizationof Fe
3
O
4
 –graphene composites as an electrode material for
a
Faculty of Applied Chemical Engineering, Chonnam National University,Gwang-ju 500-757, South Korea. E-mail: leeys@chonnam.ac.kr
b
Central Electrochemical Research Institute, Karaikudi 630006, India.E-mail: drkalpanaa@gmail.com Tel : +04565-241412
{
Electronic supplementary information (ESI) available: Experimentalprocedure, Raman spectra, SEM images, N
2
isotherms of adsorption/desorption, XPS spectra, TGA and electrochemical measurements forsingle electrodes and symmetric cells.
Cite this:
RSC Advances
, 2012,
2
, 12322–12328www.rsc.org/advances
PAPER
12322
|
RSC Adv.
, 2012,
2
, 12322–12328This journal is
ß
The Royal Society of Chemistry 2012
   D  o  w  n   l  o  a   d  e   d  o  n   0   7   D  e  c  e  m   b  e  r   2   0   1   2   P  u   b   l   i  s   h  e   d  o  n   3   1   O  c   t  o   b  e  r   2   0   1   2  o  n   h   t   t  p  :   /   /  p  u   b  s .  r  s  c .  o  r  g   |   d  o   i  :   1   0 .   1   0   3   9   /   C   2   R   A   2   1   7   1   5   E
View Article Online / Journal Homepage / Table of Contents for this issue
 
supercapacitor applications using various aqueous electro-lytes.
20,23–24
To the best of our knowledge, no reports have beenfound on the utilization of Fe
3
O
4
-based materials for symmetricsupercapacitor applications. In this work, we present, for the firsttime, the fabrication of symmetric supercapacitors based onFe
3
O
4
 –graphene nanosheet (GNS) composite materials, whichwere simultaneously compared with a pristine Fe
3
O
4
symmetriccell in 1M H
2
SO
4
electrolyte. The pristine Fe
3
O
4
and Fe
3
O
4
 –GNScomposite were prepared through a urea-assisted microwaveirradiation method followed by low temperature calcination. Theeffect of graphene on the structural and electrochemical perfor-mance of Fe
3
O
4
has been examined using various characterizationtechniques.
Result and discussion
Fig. 1 shows the XRD patterns of graphene, Fe
3
O
4
and Fe
3
O
4
 – GNS composite materials. The XRD patterns of both pristineand GNS composites exhibited peaks at the 2
h
values of 30.5, 36,43.6, 54, 57.8 and 63
u
, which corresponds to the face centeredcubic structure of magnetite particles (JCPDS no. 19–0629).
14–17
It can be seen from Fig. 1 that the composite material showedbroader peaks with lower intensity than bare Fe
3
O
4
, demon-strating that the Fe
3
O
4
 –GNS composite has a relatively lowcrystalline nature with small Fe
3
O
4
particle size, owing to thehigh degree of functional groups on the GNS surface, which isused to hinder the crystalline growth of Fe
3
O
4
grains.
26
On theother hand, the peak associated with graphene oxide (GO) orGNS was also not observed in Fig. 1 due to the high degree of disorder created in graphite to form graphene by modifiedHummers–Offeman method.
25,27
The presence of graphene in the composite material wasconfirmed by Raman analysis and the corresponding spectra arepresented as Fig. S1 in the ESI
{
. The Raman spectra obtainedfor the composite material exhibited typical carbon characteristicpeaks at
y
1350 and
y
1590 cm
2
1
, which corresponds to the Dand G band, respectively.
23
However, the pristine material didnot show such peaks within the recorded area. The G bandrelated to the symmetric E
2g
vibrations mode of C sp
2
atoms,while the D band corresponds to the breathing mode of 
-pointphonons of A
1g
symmetry.
23,24
The broadening of the D and Gbands along with a strong D line demonstrates localized in-planesp
2
domains and disordered graphitic crystal stacking of GNS.On the other hand, this considerable disorder is favorable forincreasing ionic/electronic transfer and hence a remarkableimprovement in electrochemical performance would be achievedfrom a Fe
3
O
4
 –GNS composite electrode. Therefore, the Ramanspectra, being consistent with the XRD results, furtherconfirmed the formation of the composite.The TEM images of GNS, Fe
3
O
4
and Fe
3
O
4
 –GNS wereshowed in Fig. 2. It can be clearly seen from Fig. 2a that theGNS displays a fluffy and corrugated morphology with wrinklesand protrusions. The crumbled nature formed during thesynthesis of graphene nano sheets is responsible for preventingthe aggregation of these sheets on further treatments. The TEMpicture of Fe
3
O
4
in Fig. 2b clearly demonstrates that the pristinesample consists of loosely packed irregular shaped particles of size
y
100 nm with serious agglomeration due to certain highersurface tension between the particles.
28
As can be seen from theTEM image of the Fe
3
O
4
 –GNS composite in Fig. 2c, the Fe
3
O
4
particles with a size of around 20–40 nm are homogeneouslydistributed on the surface of the GNS. Moreover, themorphology of the GNS has slightly changed from the pristineGNS, which agreed well with Fig. 1a and the SEM images (seeFig. S2 in the ESI
{
). In addition, oxygen functional groups suchas carboxylic, hydroxyl, and epoxy groups present on the GNSsurface effectively hindered the diffusion, growth and agglom-eration of Fe
3
O
4
particles in the composite.
26,27
It was alsobelieved that the van der Waals interactions and chemisorptionsbetween the nano-Fe
3
O
4
particles and GNS exist at the pristineregions of GNS and oxygen-containing defect sites.
26
Furthermore, the Fe
3
O
4
nanoparticles anchored on the surfaceof the GNS acted as spacers, which prevent the restacking of graphene sheets, thereby increasing the active surface forelectrochemical reactions.The N
2
isothermal adsorptions were presented in Fig. S3 in theESI
{
. As can be seen from the N
2
adsorption/desorptionisotherms in Fig. S3 in the ESI
{
, the Fe
3
O
4
 –GNS compositeexhibited a distinct hysteresis loop at the relative pressure
/
0
ranging from 0.4 to 1.0, which is ascribed to type IV with a type-H3 hysteresis loop, indicating the presence of a mesoporous
Fig. 1
X-Ray diffraction patterns of GNS, Fe
3
O
4
and Fe
3
O
4
 –GNScomposite powders.
Fig. 2
TEM images of (a) GNS; (b) Fe
3
O
4
; and (c) Fe
3
O
4
 –GNS (50 nmscale) composite materials prepared by using microwave synthesismethod. Scale for (a) and (b) is 100 nm.
This journal is
ß
The Royal Society of Chemistry 2012
RSC Adv.
, 2012,
2
, 12322–12328
|
12323
   D  o  w  n   l  o  a   d  e   d  o  n   0   7   D  e  c  e  m   b  e  r   2   0   1   2   P  u   b   l   i  s   h  e   d  o  n   3   1   O  c   t  o   b  e  r   2   0   1   2  o  n   h   t   t  p  :   /   /  p  u   b  s .  r  s  c .  o  r  g   |   d  o   i  :   1   0 .   1   0   3   9   /   C   2   R   A   2   1   7   1   5   E
View Article Online
 
structure.
29
Such a unique feature results in numerous openchannels for electrolyte access and facilitates the ultrafastdiffusion of ions during the cycling processes at high currentrates. The BET surface areas of Fe
3
O
4
and Fe
3
O
4
 –GNS werecalculated to be about 8.3 and 72.3 m
2
g
2
1
, respectively. It is wellknown that small particle size and high surface area areimportant parameters for any material to deliver excellentelectrochemical performances. While the small particle sizeshortens the ion diffusion resistance of the electrode–electrolyteinterface, the large surface area leads to the complete participa-tion of the active material during the charge discharge reaction.The carbon content in the Fe
3
O
4
 –GNS composite was measuredusing TGA analysis (see Fig. S4 in the ESI
{
). The carbon contentin the composite material was calculated by the weight differencebetween the Fe
3
O
4
and Fe
3
O
4
 –GNS materials at 450
u
C when allcarbon is burnt out from the composite, and the result was about9 wt%.In order to get detailed information about the surfacecomposition, XPS analysis was performed, which is verysensitive to Fe
2+
and Fe
3+
cations and the corresponding spectraare given in Fig. 3. As seen in Fig. 3a, the peaks around 711 and725 eV in higher resolution scan, Fe2p can be attributed to thelevels of Fe2p3/2 and Fe2p1/2 which is in good agreement withthose of Fe
3
O
4
.
20,22
Moreover, the satellite peak of 
c
-Fe
3
O
4
didnot appear at 719 eV, which confirmed that the electrodematerial is void of impurities and does not decompose to
c
-Fe
3
O
4
.
30
It could clearly be seen from Fig. 3b that the highresolution C 1s spectra of both GO and the Fe
3
O
4
 –GNScomposite clearly exhibited two types of major carbon peakscorresponding to carbon atoms with different functional groups.The C 1s XPS spectra of the samples showed a main peak of sp
2
graphitic carbon centered at 284.8 eV, demonstrating a success-ful reduction of GO to GNS after chemical treatment usinghydrazine. In addition, the deconvoluted C 1s XPS spectrum of GO (see Fig. S5a in the ESI
{
) has showed the C 1s of C–OH at285.9 eV, the C 1s of epoxy at 286.7 eV, the C 1s of C
L
O at 288.1eV, and the C 1s of C(O)O at 289.2 eV, respectively.
31
Thegraphene in the Fe
3
O
4
 –GNS composite reduced by hydrazinevapor exhibits the same oxygen-containing functionalities (seeFig. S5b in the ESI
{
), but their intensities are much smaller thanthat of GO. This is in agreement with the previous literaturewhich reported that the –COOH functional group could not bereduced completely through hydrazine reduction at low tem-perature.
32
The FT-IR spectra of Fe
3
O
4
and Fe
3
O
4
 –GNS compositematerials were presented in Fig. 3c. In the case of the compositematerial, the broad peak around 3500–3300 cm
2
1
could beattributed to the O–H vibrations, arising from the hydroxylgroups/water adsorbed on the GNS. The peaks at
y
2945 and2854 cm
2
1
can be assigned to the symmetric and asymmetricvibrations of C–H functional group, respectively. The strongadsorption band found at 588 cm
2
1
could be related to the Fe–Ofunctional group. It is worth mentioning here that the stretchingvibration of the carboxyl groups on the edges of the grapheneplane was not observed which demonstrated that the reductionof GO to GNS was successfully completed.
32
Additionally, theabsorption bands at 1580 and 1010 cm
2
1
were observed for theFe
3
O
4
 –GNS composite, which also confirmed the presence of C
L
C and C–O vibration of graphene, respectively.
33
This C–Obond was attributed to the defects including oxygen atoms in theGNS. Although these defects cannot be completely removedfrom the graphene structure during the chemical reduction of GO, they are useful for functionalizing the GNS composite.
34
The capacitance behaviors of the Fe
3
O
4
and Fe
3
O
4
 –GNScomposite electrodes were evaluated through cyclic voltammetryusing a three electrode cell configuration in 1 M H
2
SO
4
electrolyte in which Pt wire was used as the counter electrodeand SCE served as the reference electrode. The CV studies of Fe
3
O
4
and Fe
3
O
4
 –GNS electrodes were recorded between
2
1 to0 V at a 5 mV s
2
1
scan rate and is presented in Fig. S6a in theESI
{
. The shape of the CV curves clearly revealed that thestorage mechanism of the pristine and composite materials wasdifferent from EDLC, which is normally an ideal rectangularshape, indicating that the capacitance of Fe
3
O
4
mainly resultedfrom the redox reactions of the active material. A similar shapeof CV curves for Fe
3
O
4
was also observed in a previous report.
35
A redox reaction hump was observed around
2
0.43 V for bothpristine and composite electrodes. Although the CV curves didnot show a typical rectangular shape, it is almost symmetricalbetween the cathodic and anodic processes, which demonstratedthat both pristine and composite materials display capacitorbehavior in 1 M H
2
SO
4
electrolyte. Furthermore, the shape of the CV curves changed when the sweep rate is increased (see Fig.S6 in the ESI
{
). The possible reason for the shape changes couldbe described as follows: the distortion of current response ismainly dependent on the electrode and solution resistance, whichbecome severe at the higher current rates and hence the shape of 
Fig. 3
(a) High resolution XPS spectrum of (a) Fe 2p count of Fe
3
O
4
and Fe
3
O
4
 –GNS composite; (b) C 1 s count of graphene oxide (GO) andFe
3
O
4
 –GNS composite material; and (c) FT-IR spectrum of Fe
3
O
4
andFe
3
O
4
 –GNS nanoparticles prepared through urea-assisted microwaveirradiation method.
12324
|
RSC Adv.
, 2012,
2
, 12322–12328This journal is
ß
The Royal Society of Chemistry 2012
   D  o  w  n   l  o  a   d  e   d  o  n   0   7   D  e  c  e  m   b  e  r   2   0   1   2   P  u   b   l   i  s   h  e   d  o  n   3   1   O  c   t  o   b  e  r   2   0   1   2  o  n   h   t   t  p  :   /   /  p  u   b  s .  r  s  c .  o  r  g   |   d  o   i  :   1   0 .   1   0   3   9   /   C   2   R   A   2   1   7   1   5   E
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