Beruflich Dokumente
Kultur Dokumente
INTRODUCTION
The drastic change in weather conditions, closely depleted sources of fossil fuels and
energy shortage from all parts of the globe are just few of the motives why many are migrating to
the advancement of renewable energy technologies through sustainable and renewable energy
sources (Ginley et al., 2008). This is the reason why the evolution of energy storage system has
been sought for the past decades in order to accommodate the proper utilization of the readily
available and ample energy sources such as the wind and solar energy (Yang et al., 2011). In
association with energy storage systems, the electrochemical energy storage (EES) system is the
preeminent one. This includes batteries, fuel cells and electrochemical capacitors (ECs). One of
the rising stars in the EES is the electrochemical capacitor (EC); for this new technology showed
greater potentials than most of its competitors. ECs, also known as supercapacitors, are popular
because of their higher energy density than that of traditional capacitors and higher power
density compared to batteries. Furthermore, ECs are expected to produce high specific energy,
high specific power, long cycle life and many more, all at a low cost (Wang et al., 2012).
Supercapacitors are classified based on their charge-storage mechanisms. The first one is
the electrochemical double-layer capacitor (EDLC) which accumulates charge electrostatically
through reversible adsorption of ions of the electrolyte. The other one is the pseudo-capacitor
which utilizes fast and reversible redox reactions at the surface of the electroactive material for
charge storage (Jagadale et al., 2013). Further improvements in the capacitance of both EDLCs
and pseudo-capacitors are the center of most researches nowadays. Extensive investigation
suggests that the best way to improve the specific capacitance of both EDLC and
Conducting
Polymers
(ECPs)
are
considered
as
one
of
those
electrochemically active materials that can be used in energy storage applications. They are known
to have a pseudocapacitive characteristic, making them a viable candidate as electrode material for
supercapacitor. Compared to metal oxides, conducting polymers have outstanding advantages
namely; high conductivity, low cost, easily tuneable properties, ease of synthesis and excellent
environmental stability. Among the conducting polymers, polypyrrole (PPy) is found to be one of the
most auspicious. Several studies around the globe have proven the viability of this material as electrode
both in batteries and supercapacitor. Porous electrodes made of PPy nanosheets can be easily obtained
using electrochemical polymerization, a process which is also similar to electrodeposition of metal oxides
(Dubal et al., 2012).
Each of these electrode materials has its own unique advantages and disadvantages; for
example, carbon-based materials can provide high power density and long life cycle but its small
specific capacitance limits its application for high energy density devices (Chen and Dai, 2013).
Metal oxides/hydroxides possess pseudocapacitance in additional to double layer capacitance
and have wide charge/discharge potential range; however, they have relatively small surface area
and poor cycle life (Sun et al., 2013). Conducting polymers have the advantages of high
capacitance, good conductivity, low cost and ease of fabrication but they have relatively low
mechanical stability and cycle life (Ma et al., 2014). Coupling the unique advantages of these
nano-scale dissimilar capacitive materials to form nanocomposite electroactive materials is an
important approach to control, develop and optimize the structures and properties of electrode
material for enhancing their performance for supercapacitors (Chen et al., 2014). The properties
of nanocomposite electrodes depend not only upon the individual components used but also on
the morphology and the interfacial characteristics (Bavio et al., 2014). Recently, considerable
efforts have been placed to develop all kinds of nanocomposite capacitive materials, such as
mixed metal oxides, conducting polymers mixed with metal oxides, carbon nanotubes mixed
with conducting polymers, or metal oxides, and graphene mixed with metal oxides or conducting
polymers (Staaf et al., 2014). Design and fabrication of nanocomposite electroactive materials
for supercapacitors applications needs the consideration of many factors, such as material
selection, synthesis methods, fabrication process parameters, interfacial characteristics, electrical
conductivity, nanocrystallite size, and surface area, etc. (Liu et al., 2014). Although significant
progress has been made to develop nanocomposite electroactive materials for supercapacitor
applications, there are still a lot of challenges to be overcome.
Despite of the present technology and availability of materials, an electrode that would
surpass or somehow par the energy density offered by the battery has not been realized. The general
objective of this study is to fabricate a composite material of cobalt oxide and PPy on flexible substrate.
Specifically, this study aims (1) to synthesize polypyrrole and cobalt oxide via direct
electrochemical co-deposition, (2) to characterize the morphology; structural property and
electrochemical property of synthesized materials, (3) to assess the characteristics of the
composite electrode (4) employ the synthesized composite material in a device prototype and
evaluate its performance.
Results of this study can help provide alternative nanomaterials with promising
characteristics for the improvement of specific capacitance of capacitors The significance of the
study is to develop an enhanced composite material by combining the synthesized polypyrrole
and cobalt oxide. The research may help to produce new materials to be used in possible
applications.
The study will be limited to synthesizing and characterizing the given conducting
polymer and the metal oxide, which is polypyrrole and cobalt oxide; together with the composite
material of polypyrrole-cobalt oxide, respectively. This study will not cover the production of a
prototype supercapacitor of the said materials.
Chapter 2
REVIEW OF LITERATURE
specific capacitance and energy density than EDLCs, but are also known to have poor cycle
ablity (Huang et al., 2014). Meaning to say, supercapacitors are hindered by their energy
density value, which is still much lower than that of batteries, in achieving their full potentials in
different applications. Therefore, what we need to do in order to meet the future energy demands
is to boost the energy density of supercapacitors without sacrificing its excellent power density
(Hung et al., 2014).
The focus of many researches nowadays is the further development of the electrode
materials for the supercapacitor since this size up the performance of the supercapacitor.
For the synthesis of the supercapacitor electrode, the major ingredients that are widely
used are carbon materials, transition-metal oxides, and conducting polymers (Chen et al.,
2014). Unfavorably, all of these materials give challenge to researchers because they all have
their own drawbacks. For electrode made of carbon materials, they are known to physically
store only minimal amounts of charges which may cause them to only have low specific
capacitance. Electrode made of conducting polymers on the other hand may swell and
shrink during the process which is the reason of its low cycle life. Lastly electrode made of
transition-metal oxides may show low specific surface area, poor electronic and ion
conductivity limiting the supercapacitor power density. In order to address the lack of one,
many researches combined the different materials to compensate each other (Wang et al.,
2012). The introduction of metal oxides in carbon materials offers the benefits of both the
faradaic capacitance of the metal oxide and the double layer capacitance of the carbon
materials with large specific surface areas, thereby improving the capacitance and energy/power
capabilities (Manikandan et al., 2001). When these transition metals are reduced in their nanosized structure, they are expected to improve in terms of their electrical and mechanical
properties such as electrical conductivity and strength. Nanostructured electrodes have high
surface area which contributes in the increased performance of the supercapacitor electrode
(Wallace et al., 2009).
Several metal oxide thin films such as nickel oxide (Ge et al., 2013), manganese oxide
(Yu et al., 2011), iron oxide (Du et al., 2009), ruthenium oxide (Ramani et al., 2001), cobalt
oxide (Xia et al., 2011), and many more are investigated as alternative electrode materials. All of
the materials stated beforehand reportedly come up with pros and cons. Both nickel oxide and
iron oxide has low cost, easy to synthesize, environmentally friendly, and has high theoretical
specific capacitance. Though the poor conductivity of nickel oxide has limited its capacitance to
low value, and hindered the fast electron transport required for high charge/discharge rates
(Huang et al., 2014). While the insulating nature for Fe3O4 severely hinders its charge storage
capability to be used as an electrode of supercapacitor (Guan et al., 2013). Another one is
manganese oxide which is popular for its pseudocapacitive properties and is also known to be
environmentally friendly and less costly. The drawback is the low power density due to the low
electronic conductivity of manganese oxide (Straiti and Lufrano, 2010). While ruthenium oxides
are known to provide relatively high specific capacitance with remarkable cycle life but are also
very costly and toxic in nature thats why its application and commercialization has slowed down
(Liu et al., 2010). Lastly, the most stable phase of cobalt oxide which is Co 3O4, can be a suitable
electrode material due to its low cost, high reversibility and high theoretical specific capacitance
(Cheng at al., 2010).
Cobalt Oxide
Cobalt oxide (Co3O4) is one type of electrode materials used in supercapacitors. Liu et al.
reported that cobalt oxide shows great potential as an electrode for supercapacitors (B.O. Park et
al., 2004). They are found in several forms and had been studied because of its properties as a
strong candidate for a supercapacitor electrode. They have distinct characteristics like being
environment friendly and inexpensive. According to Srinivasan and Weidner, Co3O4 is behaving
like a capacitor (V. Srinivasan et al., 2002). Other cobalt compounds have been studied because
of their large energy density. Capacitors, including CoOx, Co 3O4 andCo(OH)2, have also been
studied because of their larger energy densities (C. Lin et al., 1998). Cobalt oxides are useful
materials applied in various fields such as in rechargeable batteries (F. Lichtenberg et al.,
1996), as a magnetic material catalysis(S.A. Makhlouf et al., 2002), energy storage and
magnetism. On the other hand, in the production of electrode, cobalt oxides with thick films
result in low densities and unsuccessful use for cobalt oxide capacitors. For that reason, the
approach should be to enhance its characteristics on conductivity, specific area and
densities by reducing its size into the nano-scale (P. Lin et al., 2010). Nanostructured
materials are known to possess great advantages over their bulk counterparts in fulfilling
both high energy density and high power density because nanostructures would provide more
effective electroactive sites for charge storage, shorter solid path lengths for ion diffusion and
electron transfer, and faster kinetics for rate capability (Wang et al., 2014).
Preparation of cobalt oxide
Some of the methods in preparing cobalt oxides were the spray pyrolysis, sputtering,
chemical vapor deposition (CVD), spin-coating preparation (Wang et al., 2011), electrospray
deposition (A.Jaworek et al., 2008) and solgel process (V.R. Shinde et al., 2006).
Electrospray is the best method for the deposition of cobalt oxide films (O. Kilo et al.,
2014). Furthermore, Chemical deposition is also a promising method; it requires no complicated
materials or instruments, and chemical to be used are inexpensive and normally accessible. This
method deposits large-area films on non-planar substrates that are not stable at different high
temperatures (Kandalkara et al., 2010). To characterize cobalt oxides, series of methods can be
used, these are the Temperature-programmed decomposition (TPD), X-ray diffraction (XRD),
infrared spectroscopy (IR), Raman spectroscopy and temperature- programmed reduction (TPR).
Morphologies of cobalt oxides may be based on the analysis of using the selected-area
electrondiffraction (SAED) and X-ray diffraction (XRD) (Chih-Wei Tangaet al., 2008). Other
works used scanning electron microscopy (SEM to study the surface morphology of the oxide
and also made use of the cyclic voltammetry and galvanostic charge discharge method to be
able to investigate the capacitive properties of thin cobalt oxide films (Kandalkaret al., 2008).
506 F/g which is higher than those of carbon based electrodes (L.L. Zhanget al., 2009). Even
though an expensive metal like the ruthenium oxide is with higher capacitance, PPys when
synthesized by different dopants such as ptoluene sulphonic acid (R. Ramya et al., 2008),
chromotropic acid (D.K. Ariyanayagamkumarappa et al., 2012) , 5sulfosalicylic acid ( X.Li et
al., 2012) , sulfanilic acid (S.Chen et al., 2013), and many others, also when sodium dodecyl
benzene sulfonate (M.D. Ingram et al., 2004),a surfactant is there, could provide the PPy a
specific capacitance as high as those expensive metals. Some reports showed by using
polycharges aromatic kind of dopants we may be ableto improve the polyppyrroles stability and
also its conductivity (B. Weng et al., 2011). Moreover, the increase in capacitance of the Ppy is
proportional to that of the increasing dimension of the dopant molecules (Y. Zhu et al., 2013).
These polymers stands out from all others because they are environment friendly and chemically
stable as well, which makes it very ideal such that many are being interested in studying these in
relation of its use in supercapacitors (S. Sahoo et al., 2013).
Chapter 3
METHODOLOGY
of the cobalt oxide film will be investigated by cyclic voltammetry (CV) and galvanostic charge
discharge methods in 1.0 M KOH aqueous solution. In the characterization, a typical three
electrode cell will be used. The cobalt oxide will act as working electrode and a platinum
electrode will be used as counter electrode. This experiment will be done at room temperature
and potential values that will be used are with respect to that of saturated calomel electrode
(SCE).
The morphologies of the cobalt oxide will be examined using a scanning electron
microscope equipped with a cold field emission electron gun. The structure will be characterized
by a transmission electron microscope (TEM). The phase and crystalline structure will analyzed
by X-ray diffraction (XRD) using Cu Ka radiation.
Preparation of Polypyrrole
Polyppyrolle will be prepared via electrochemical route. Briefly, a three electode system
will be used. Pt will serve as counter electrode, Ag/AgCl will serve as the reference electrode and
Ni foam/ITO coated PET will serve as the working electrode. 0.1 M of LiClO4 will be used as
the supporting electrolyte. Cyclic voltammetry will be employed in electrodepositing Ppy on the
working electrode. The potential will be cycled from 0volts to 1.2volts for 15 times using
50mV/s as scan rate.
REFERENCES:
D. Ginley, M. A. Green, R. Collins, MRS Bulletin 33 (2008); 355
Z. Yang, J. Zhang, M. C. W. Kintner-Meyer, X. Lu, D. Choi, J. P. Lemmon and J. Liu,
Electrochemical Energy Storage for Green Grid, Chemical Reviews 111, (2011) 3577-78
G. P. Wang, L. Zhang, J.J. Zhang, A review of electrode materials for electrochemical
supercapacitors, Chemical Society Reviews 41 (2012); 797-799
PornsitLorkit et al., Iron oxide-based supercapacitor from ferratrane precursor via solgelhydrothermal process, Energy Procedia 56 (2014); 466 473
L. Feng et al., Recent progress in nickel based materials for high performance pseudocapacitor
electrodes, Journal of Power Sources 267 (2014); 430-444
B. Vidyadharan et al., High energy and power density asymmetric supercapacitors using
electrospun cobalt oxide nanowire anode, Journal of Power Sources 270 (2014) 526-535
K.-J. Huang et al., One-step synthesis of layered CuS/multi-walled carbon nanotube
nanocomposites for supercapacitor electrode material with ultrahigh specific capacitance,
ElectrochimicaActa 149 (2014) 2833
C.J. Hung et al., High energy density asymmetric pseudocapacitors fabricated by
graphene/carbon nanotube/MnO2 plus carbon nanotubes nanocomposites electrode, Journal of
Power Sources 259 (2014) 145-153
Jun Chen, ChunyangJia, Zhongquan Wan, Novel hybrid nanocomposite based on poly(3,4ethylenedioxythiophene)/multiwalled carbon nanotubes/graphene as electrode material for
supercapacitor, Synthetic Metals 189 (2014) 6976
X. Ge, C.D. Gu, Y. Lu, X.L. Wang, J.P. Tu, J., Mater. Chem. A 1 (2013) 13454-13461
G. Yu, L. Hu, N. Liu, H. Wang, M. Vosgueritchian, Y. Yang, Y. Cui, Z. Bao, Nano
Lett. 11 (2011) 4438-4442
X.H. Xia, J.P. Tu, X.L. Wang, C.D. Gu, X.B. Zhao, Chem. Commun. 47 (2011)
5786-5788.
X. Du, C. Wang, M. Chen, Y. Jiao, J. Wang, J., Phys. Chem. C 113 (2009) 2643-2646
Ramani M, Haran BS, White RE, Popov BN, Synthesis and characterization of hydrous
ruthenium oxidecarbon supercapacitors, J ElectrochemSoc 2001;148:A37480
Ramani M, Haran BS, White RE, Popov BN, Arsov L. Studies on activated carbon capacitor
materials loaded with different amounts of ruthenium oxide. Journal of Power Sources 2001; 93:
20914
Hwang S-W, Hyun S-H, Synthesis and characterization of tin oxide/carbon aerogel composite
electrodes for electrochemical supercapacitors. J Power Sources 2007; 172: 4519
Zhang W, Qu YH, Gao LJ., Performance of PbO2/activated carbon hybrid supercapacitor with
carbon foam substrate, Chin ChemLett 2012;23: 623626
P. Staiti, F. Lufrano, Investigation of polymer electrolyte hybrid supercapacitor based on
manganese oxidecarbon electrodes, ElectrochimicaActa 55 (2010) 74367442
Dahui Guan, ZanGao, Wanlu Yang, Jun Wang, Yao Yuan, Bin Wang, Milin Zhang, Lianhe Liu,
Hydrothermal synthesis of carbon nanotube/cubic Fe3O4 nanocomposite for enhanced
performance supercapacitor electrode material, Materials Science and Engineering B 178 (2013)
736743
J. Liu, J. Essner, J. Li, Hybrid supercapacitor based on coaxially coated manganese oxide on
vertically aligned carbon nanofiber arrays, Chem. Mater. 22 (2010) 50225030
E.W. Paul,A.J. Ricco and M.S. Wrighton, Conducting polymers as active materials
inelectrochemical capacitors,Phys. Chem., 89 (1985) 1441
Andy Rudge, John Davey, Ian Raistrick and ShimshonGottesfeld, Journal of Power Sources, 47
(1994) W-107
S. Lu, S.S. Wang, X.M. Li, T. Feng, L.J. Guo, X.H. Zhang, D.S. Liu, T. He, J. Mater.
Chem. A 2 (2014) 12805-12811
L.L. Zhang, X.S. Zhao, Carbon-based materials as supercapacitor electrodes, Chem. Soc. Rev. 38
(2009) 25202531.
R. Ramya, M.V. Sangaranarayanan, Analysis of polypyrrole-coated stainless steel electrodes Estimation of specific capacitances and construction of equivalent circuits, J. Chem. Sci.
(Bangalore, India) 120 (2008) 2531.
D.K. Ariyanayagamkumarappa, I. Zhitomirsky, Electropolymerization of polypyrrole films on
stainless steel substrates for electrodes of electrochemi-calsupercapacitors, Synth.Met. 162
(2012) 868872.
X. Li, P. Imin, A. Adronov, I. Zhitomirsky, Effect of 5-sulfosalicylic acid and poly [2,5-bis(3sulfonatopropoxy)-1,4-ethynylphenylene-alt-1,4-ethynylpheny-lene] on electrodeposition of
polypyrrolecarbon nanotube films on stainless steel, Mater. Lett. 68 (2012) 2427.
S. Chen, I. Zhitomirsky, Polypyrrole electrodes doped with sulfanilic acid azochromotrop for
electrochemical supercapacitors, J. Power Sources 243 (2013) 865871.
M.D. Ingram, H. Staesche, K.S. Ryder, Activated polypyrrole electrodes for high-power
supercapacitor applications, Solid State Ionics 169 (2004) 5157.
B. Weng, R. Shepherd, J. Chen, G.G. Wallace, J. Mater. Chem. 21 (2011) 1918-1924.
Y. Zhu, I. Zhitomirsky, Preparation of polypyrrole thin film counter electrode with prestorediodine and resultant influence on its performance, Synth. Met. 185 (2013) 126-132
Shan Lu a, b, c, Xuehua Zhang, Ting Feng d, Ruobing Han a, Dongsheng Liu c, Tao He a,
Journal of Power Sources 274 (2015) 1076-108
B.O. Park, C.D. Lokhande, H.S. Park, J. Power Sources 134 (2004) 148.