Electrochimica Acta 53 (2008) 76907695

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Manganese oxide embedded polypyrrole nanocomposites for electrochemical supercapacitor

R.K. Sharma, A.C. Rastogi 1 , S.B. Desu ,1
201, Marcus Hall, Department of Electrical and Computer Engineering, University of Massachusetts, Amherst, MA 01003, USA

a r t i c l e

i n f o

a b s t r a c t
MnO2 embedded PPy nanocomposite (MnO2 /PPy) thin lm electrodes were electrochemically synthesized over polished graphite susbtrates. Growing PPy polymer chains provides large surface area template that enables MnO2 to form as nanoparticles embeded within polymer matrix. Co-deposition of MnO2 and PPy has a complimentary action in which porous PPy matrix provides high active surface area for the MnO2 nanoparticles and, on the other hand, MnO2 nanoparticles nucleated over polymer chains contribute to enhanced conductivity and stability of the nanocomposite material by interlinking the PPy polymer chains. The MnO2 /PPy nanocomposite thin lm electrodes show signicant improvement in the redox performance as cyclic voltammetric studies have shown. Specic capacitance of the nanocomposite is remarkably high (620 F g1 ) in comparision to its constituents MnO2 (225 F g1 ) and PPy (250 F g1 ). Photoelectron spectroscopy studies show that hydrated manganese oxide in the nanocomposite exists in the mixed Mn(II) to Mn(IV) oxidation states. Accordingly, chemical structures of MnO2 and PPy constituents in the nanocomposite are not inuenced by the co-deposition process. The MnO2 /PPy nanocomposite electrode material however shows signicantly improved high specic capacitity, chargedischarge stability and the redox performance properties suitable for application in the high energy density supercapcitors. 2008 Published by Elsevier Ltd.

Article history: Received 1 March 2008 Received in revised form 31 March 2008 Accepted 2 April 2008 Available online 18 April 2008 Keywords: MnO2 nanocomposite Polypyrrole Supercapacitor Specic capacitance

1. Introduction Electrochemical supercapacitor is a charge storage device that can withstand higher power compared to the battery, and deliver higher energy compared to the conventional or electrolytic capacitor [13]. Supercapacitors are classied into two types based on their charge storage mechanism; electrical double layer (EDL) capacitors and the pseudo-capacitors. Energy storage in EDLC is due to charging of the electrical double layer at the electrode and electrolyte interface however a pseudo-capacitor utilizes faradic reactions in addition to double layer charge. Carbon materials have been widely investigated for ELD capacitor whereas the charge storage in such materials is limited due to electrostatic in origin. Redox metal oxides (RuO2 and MnO2 ) have shown high performance as electrode material in supercapacitor [48]. The high cost, low porosity and rapid decrease of power density at high

Corresponding author. Tel.: +1 607 777 4030; fax: +1 607 777 4822. E-mail addresses: drrajksharma@yahoo.co.in (R.K. Sharma), rastogi@ecs.umass.edu, arastogi@binghamton.edu (A.C. Rastogi), sdesu@ecs.umass.edu, sdesu@binghamton.edu (S.B. Desu). 1 Present address: Department of Electrical and Computer Engineering, Binghamton University, State University of New York, Binghamton, NY 13902, USA. 0013-4686/$ see front matter 2008 Published by Elsevier Ltd. doi:10.1016/j.electacta.2008.04.028

charge discharge rates however are disadvantages of using RuO2 . In recent years increasing attention is given to the hydrous manganese oxides (MnO2 xH2 O). The specic capacitance reported for MnO2 is 250 F g1 and a high capacitance (1370 F g1 ) is projected at very low loading levels when the material utilization is high [9,10]. There are efforts to enhance the material utilization by using large area supports or by forming composites of MnO2 [11,12]. Direct deposition of MnO2 on carbon blacks with large surface area, nanotubes, activated or meso porous carbons have been studied to increase active surface area of MnO2 [1115]. The large area supports are effectively shown to prevent the MnO2 agglomeration and thus keeping a high active surface area of the adsorbed material. Besides providing the support, carbon materials with large surface area (2500 m2 /g) could also store higher charge and thus have been widely investigated for EDL capacitors [16,17]. However, application of carbon materials in EDLC is limited due to the micropores that are not easily wetted by electrolytes and a large part of the exposed carbon surface may not be utilized for charge storage [18]. Furthermore, carbon material is also found to suffer from slow deterioration by oxidation which increases internal resistance [1]. In contrast to the existence of various oxidation structures, conducting polymers have appeared as a potent choice for supercapacitor electrode material [1,2,19]. Polypyrrole (PPy), an important conducting polymer has been successfully employed as redox

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electrode material [2022]. In spite of the high charge storage capabilities, PPy and other conducting polymers are lacking in long-term stability and mechanical properties [23]. A unique combination of the metal oxide particulates dispersed over large surface area with conducting polymer as support appears interesting for supercapacitor electrodes. In the present work, we report on the nanostructured MnO2 particles embedded within PPy matrix (MnO2 /PPy) as a composite electrode material prepared by the electrochemical co-deposition technique. In the past composites of redox metal oxides have been prepared by several methods like physical mixing or dispersion in the solution; however we show by the electrochemical co-deposition process for MnO2 and PPy in which Mn2+ ions were provided in the monomer pyrrole solution during galvanostatic polymerization can effectively produce a nanocomposite material. The process basically involves anodic growth of two different chemical entities; polypyrrole by polymerization and the anodic oxidative deposition of MnO2 nanoparticles which become electro-embedded within the growing polypyrrole polymeric chain structures. Electrochemical performance of these two chemical entities is interrelated and has a complimentary action. PPy provides enormously large surface area for dispersion that helps MnO2 to grow in the form of nanosize particles with a high active surface area for redox processing. In turn, the MnO2 particles provide a rigid support and a percolated electrical conducting path to PPy by interlinking the polymer chains thus providing improved charge exchange efciency and stability during redox cycling. This paper reports on the synthesis, electrochemical and morphological properties of the MnO2 /PPy nanocomposite electrodes for the supercapacitors. 2. Experimental High purity chemicals; the pyrrole monomer, MnSO4 5H2 O, Na2 SO4 salts and H2 SO4 solvent were procured from Aldrich. Deionised water was used to prepare the electrochemical solutions for electrodic lm growth and characterization. Monomer pyrrole (0.1 M) in 0.5 M H2 SO4 was used for the growth of polymer lm. To deposit MnO2 /PPy nanocomposite lms, electrochemical polymerization of pyrrole and MnO2 layer formation were simultaneously carried out by adding 0.2 M MnSO4 to the solution. All the potentials were measured against saturated Ag/AgCl reference using platinum plate as counter electrode. Polished graphite plates (1 cm2 ) were used as working electrode. MnO2 /PPy was electrochemically co-deposited under galvanostatic conditions by applying constant current density (4 mA cm2 ) for a xed duration 200 s. Pure MnO2 and PPy electrodes were also electrodeposited from the solutions carrying Mn or PPy precursors separately as reference material to the MnO2 /PPy nanocomposite. Deposition current density, electrolyte pH and the growth time was kept identical for each deposition and the amount of total charge used in the lm growth was kept constant. Followed by the growth, electrodes were rinsed in deionised water and dried prior to electrochemical evaluation of specic capacitance by cyclic voltammetry in 0.5 M Na2 SO4 solution. The electrodes were tested between 0.5 and 0.5 V (Ag/AgCl) in three-electrode electrochemical cell using potentiostat (Solartron model 1260). Chemical composition and surface microstructure of the electrodic deposits were analyzed by X-ray photoelectron spectroscopy (XPS) and eld emission scanning electron microscope (FESEM). 3. Results and discussion Specic capacitance of the deposited materials was evaluated by cyclic voltammetric analysis in 0.5 M Na2 SO4 solution. Cyclic

Fig. 1. Cyclic voltammogram (a) PPy, (b) hydrous MnO2 and (c) MnO2 /PPy nanocomposite electrode at 50 mV s1 in 0.5 M Na2 SO4 .

voltammograms recorded for hydrous MnO2 , PPy and PPy/MnO2 composite electrode are shown in Fig. 1. PPy/MnO2 composite electrode exhibits high out put current in comparision to the electrodes of MnO2 and PPy prepared under identical conditions. Typically, the PPy/MnO2 composite electrode showed much higher specic capacitance (600 F g1 ) when compared to 200250 F g1 of the electrodes made by the constituent materials. The enhancement in the charge strorage capacity of the composite material is attributed to the structural modications of constituents MnO2 and PPy as shown later. Deviation from rectangular shape of voltammogram of MnO2 /PPy nanocomposite is due to polarization resistance. The XPS surface scan spectra of the PPy/MnO2 composite lm deposited over Pt substrate after having been subjected to the oxidationreduction cycle in a 0.5 M Na2 SO4 aqueous electrolyte was studied. Formation of the nanocomposite by manganese oxide incorporation within electro-polymerized PPy is evidenced by manganese Mn2p3/2 and satellite Mn2p1/2 along with oxygen O1s XPS peaks as shown in Figs. 2 and 3. An assessment of the Mn-oxide component contribution to the pseudo-capacitance towards improving the overall electrochemical performance of the nanocomposite electrode requires a precise knowledge of the oxi-

Fig. 2. Mn2p core level XPS spectra showing existence Mn(II) and Mn(IV) in the MnO2 /PPy nanocomposite lm.

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Fig. 3. O1s core level XPS spectra and deconvoluted peak positions corresponding to MnO, MnOH and SO4 2 bonded oxygen in MnO2 /PPy nanocomposite lm.

dation state of Mn. The Mn2p and O1s core level spectra were therefore analyzed to determine Mn-oxide phases present within PPy matrix. The Mn2p3/2 and Mn2p1/2 transitions are centered at 642 and 653.4 eV, respectively, as shown in Fig. 2. Contributions from different Mn species were distinguished by curve tting using the LorentzGaussian prole procedure. Deconvoluted Mn2p3/2 peaks at 640.8 and 642.0 eV having spin energy separation of 12.6 and 11.4 eV with the satellite Mn2p1/2 peak are attributed to the presence of Mn(II) and Mn(IV) oxide phases, respectively, consistent with the reported data for Mn3 O4 and MnO2 [24]. Existence of the Mn-oxide phases is also reected in the O1s core level

spectra shown in Fig. 3. The binding energy separation between the O1s oxide component peak and the Mn2p3/2 peak for Mn(IV) is 112.0 eV which is an indication of MnOMn bonding structure [25,26]. The Mn(II) to Mn(IV) ratio in the lm is 1:1.39 as determined from the area under the XPS peaks. Aqueous electrodeposition studies reported earlier [25] show growth of stable Mn3 O4 and MnO2 lms occur in two different potential regimes. In the present case, initial electro-polymerized PPy nanocomposite lm probably contained mostly MnO2 phase because the electrodeposition conditions favored it. The Mn(IV) is reduced to Mn(II) during the electrical analysis of the nanocomposite supercapacitor while undergoing the electrochemical dedoping step. Since both Mn(II) and Mn(IV) phases coexist, the electrode perhaps represents a state of incomplete reduction step. These observations suggest that nanodispersed MnO2 within the PPy matrix also actively participates in the redox pseudo-capacitive reaction with the involvement of the ionic species from the Na2 SO4 electrolyte used in the study of the supercapacitor made from such electrodes. Similar results were inferred from MnO2 based supercapacitors [10]. Clearly, the nanodispersed MnO2 also contributes to the charge storage simultaneously to the PPy conducting polymer. This aspect is further discussed in later sections. Deconvolution of the O1s XPS spectra (Fig. 3) indicates three different oxygen bonding congurations, such as MnOMn oxide bonding at 530.3 eV, MnOH hydroxyl bond at 531.2 eV and HOH molecule or SO4 2 bonded oxygen at 532.1 eV [25]. A substantial fraction 43.5% of the mean oxygen concentration in the lm determined from XPS O1s peak is bonded as SO4 2 . In conjunction with the sulphur (S) concentration at 14.2% determined from S2p XPS peak, this indicates high concentration of SO4 2 ions trapped within the MnO2 embedded PPy nanocomposite electrode system as expected for the nanocomposite electrode in the oxidative (doping) state. During the PPy electrode doping process Mn(II) oxidation

Fig. 4. FESEM micrographs of the electrodic lms grown under identical conditions (a) PPy, (b) MnO2 , (c) MnO2 /PPy nanocomposite and (d) MnO2 embedded PPy composite at high magnication.

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to Mn(IV) involves complex intermediate steps such as formation of Mn(II) hydroxide, MnOOH or Mn-(OH)2 polymorphs instead of direct MnO2 as described in some earlier studies [27]. Proton promoted reaction of MnOOH, Mn(OH)2 in the acidic medium produces MnO2 [28]. Oxygen present as OH basically represents intermediate MnOOH stage. The relative intensity of the three oxygen bonded structures indicates a transitional process of Mn-oxide between the reduction and re-oxidation states. As inferred earlier, pseudo-capacitance storage due to change in valence state of Mn contributes to the overall high specic capacitance 620 F g1 of the nanocomposite electrode. Porosity of the electrochemical electrode is an important parameter for attaining high charge density by area enhancement. The FESEM micrograph of (a) PPy, (b) hydrous manganese oxide and (c) the MnO2 /PPy nanocomposite prepared under indentical conditions of current density and growth time are presented in Fig. 4. Electro-polymerized PPy lm show highly porous morphology as seen by the micrograph (a). Such polymer morphology of electro polymerized PPy has been reported by other groups as well [29]. The morphology of the electrodeposited manganese oxide shown in micrograph (b) is relatively dense with a cauliower like agglomerated clusters of MnO2 particles. Micrograph (c) for the MnO2 /PPy nanocomposite shows remarkable features which is basically dominated by PPy morphology and the MnO2 , rather than forming a dense microstructure as in the micrograph (b) is seen embeded in PPy scaffold in the form of 100 nm nodular grains. The high magnication picture (micrograph (d)) clearly show the MnO2 nanograins embeded in PPy. The MnO2 /PPy nanocomposite morphology observed in Fig. 4 (micrograph c and d) clearly show the evolution of large surface area of the co-deposited MnO2 .Considering the voltammometric response, composition analysis and the morphological features in Figs. 14, it is inferred that the PPy and MnO2 have complimentry action during the growth of electrodic lm and its redox cycling. During the growth of MnO2 /PPy nanocomposite electrode by electrochemcial co-deposition, the PPy due to its porous morphology provides a large surface to the growing MnO2 enabling a high active surface area of the MnO2 particles. Simultaneously, the nucleation of MnO2 nanoparticles over growing polypyrrole chains terminates its further growth by attachment and gives rise to a fresh nucleation of PPy chain on the same or at another site. PPy structure is an important parameter as the shorter and ordered polymer structure are found to be ideal structures for charge storage [30]. Furthermore, the presence of MnO2 in PPy scaffold enhances the conductivity of composite by cross linking the PPy chains. This signicantely reduces the chain defects responsible for hopping conduction [31]. Additionally, the MnO2 particle clusters in the polymer matrix essentially provide rigid support for stability of the PPy chains during redox cycling. The pseudo-capacitance of MnO2 signicantly depends on the surface atoms and in the MnO2 /PPy nanocomposite, the available large surface of supported/embeded MnO2 nanoparticles signicantly contribute to the overall capacitance. Therefore, the large surface area of the embeded MnO2 nanoparticles as well as structurally modied PPy polymer chains due to MnO2 nucleation both contribute to the high specic capacitance of the nanocomposite synthesized by electrochemical co-deposition. As discussed earlier, based on XPS data in Fig. 2, in the PPy doping process Mn(II) oxidation to Mn(IV) through complex intermediate steps involves formation of hydrous Mn(II) hydroxide, MnOOH or Mn(OH)2 polymorphs instead of direct MnO2 . In earlier reports the redox process of Mn is shown to involve the (III) and the (IV) oxidation states of Mn [10], however in the present co-deposition process nanoMnO2 allowed redox involvement of Mn(II) and Mn(IV) oxidation states. The phase change of MnO2 to various oxidation states of hydrous manganese oxides is associated with the electron

exchange, therefore the redox process between Mn(II) and Mn(IV) instead of Mn(III) and Mn(IV) involves an additional oxidation state and consequently an improved charge storage capacity. There are two mechanisms proposed for charge storage in faradic redox supercapacitor electrodes. The rst is based on the intercalation of H+ or Na+ ions in the electrode during reduction and deintercalation on oxidation [1,6]. MnO2 +H+ + e MnOOH (1)

The other is adsorption of cations on the electrode surface from electrolyte. (MnO2 )surface + C+ + e (MnO2 C+ )surface (2)

The redox processes in polypyrrole involve mass and resistance change as well as electron transitions unlike the other redox systems in electrochemistry where only electrons are involved. The oxidation of polypyrrole called doping, yields a charged polymer lm with incorporated anions and during reduction (dedoping) these anions are expelled. Polypyrrole contains a cationic polymer backbone, hence the PPy units have a positive charge and the anions are used as charge compensating ion in redox process. It is interesting in MnO2 /PPy composite that the charge storage of MnO2 utilizes the cations from electrolyte however the anions are involved as charge compensating ions in PPy. Mass transport property of the electrode depends on the morphology of the electrodic deposit, conditions of lm preparation, nature of counter ion, etc. The electrode capacitance depends primarily on the crystalline structure of the material and its morphology, especially on pore size as porous channels are able to overcome the limitations on the charged ion intercalation (doping) or adsorption [32]. During potential cycling, increase in scan rate has a direct impact on the diffusion of electrolyte ions into the electrode material matrix. At higher scan rates the working ions will only approach the outer surface of the electrode and hence the material that is accessible only through the deep pores does not actively contribute to pseudo-capacitance. In order to understand the electrochemical performance of the MnO2 /PPy nanocomposite electrodes, cyclic voltammograms were recorded at different scan rates. Fig. 5a shows a set of CV curves for the MnO2 /PPy nanocomposite electrode showing a decrease in specic capacitance with increase in the scan rates. Compilation of the data on the specic capacitance change with scan rates for PPy and MnO2 electrodes is presented in Fig. 5b. Potential cycling at high scan rates typically causes the electrolyte ions to only reach the outer surface and consequently a decrease in the pseudo-capacitance is expected. As seen in Fig. 5a, the specic capacitance of MnO2 /PPy nanocomposite electrode at different scan rates shows that specic capacitance fades from 62026 F g1 . This decrease in specic capacitance at high scan rate is due to some polarization indicating that all the electrode material is not fully charged or discharged due to limited ionic diffusion in the electrode material. According to Fig. 5b specic capacitance decline in MnO2 /PPy nanocomposite is 31% compare to available specic capacitance measured at low scan rate at 5 mV s1 but a comparatively much higher decline is seen for MnO2 and PPy electrodes as 65 and 44%, respectively. The improved performance of the MnO2 /pPy composite electrode is attributed to the enhanced surface area (porosity) of the material. Subsequently, even on high scan rates higher concentration of working ions is still able to access the active regions of PPy chains and MnO2 active sites, so decrease in the pseudo-capacitance takes place to a much lesser extent. In order to understand the total charge storage capacity of MnO2 /PPy nanocomposite electrode, total voltammetric charges have been studied as a function of scan rate. As presented in Fig. 6a the voltammetric charge q* decreases with the increase in scan rate

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Fig. 5. Scan rate dependence of MnO2 /PPy composite electrode in 0.5 M Na2 SO4 ; (a) 5 mV s1 , (b) 20 mV s1 , (c) 50 mV s1 and (d) 100 mV s1 . (b) Effect of scan rate on the specic capacitance of MnO2 /PPy, MnO2 and PPy electrodes in 0.5 M Na2 SO4 .

Fig. 6. Variation of voltammetric charge (q* ) in MnO2 /PPy composite as a function of scan rate v; (a) extrapolation of q* to v = from the q* vs v1/2 plot gives the outer charge q (charge on the most accessible active surface of MnO2 /PPy composite); O (b) extrapolation of q* to v = 0 from the 1/q* vs v1/2 plot gives the total charge q T (charge related to the whole active surface MnO2 /PPy composite).

(v). In the reversible redox process, the dependence of q* on v can be explained by the slow diffusion of working ions within the pores of the electrode material. At high scan rate, the diffusion limitation slows down the accessibility of ions to the inner regions of the electrode material, except for more accessible outer surface regions where the diffusion of ions is not hampered [25,3337]. The extrapolation of q* to v = (v1/2 = 0) from the q* vs v1/2 (Fig. 6a) gives the outer charge q , 425 C g1 , which is the charge due to redox O process on most accessible active surface [35]. The extrapolation of q* to v = 0 from 1/q* vs v1/2 plot in Fig. 6b gives the total charge q , T 714 C g1 which is the charge related to the entire active surface of the MnO2 /PPy nanocomposite. The ratio (q q )/q suggests that T T O nearly 60% of the inner and outer surface region of the electrochemically co-deposited MnO2 /PPy nanocomposite materials is available for the charge storage. A similar study carried out for the similarly deposited PPy and MnO2 electrode shows (q q )/q 0.54 and T T O 0.79 implying 46 and 21% of the inner and outer combined surface regions are redox active for charge storage. The life cycle test of the PPy, hydrous MnO2 and MnO2 /PPy nanocomposite electrodes in the supercapacitor device structure were carried out after sequential chargedischarge cycling at a con-

Fig. 7. Life cycle test of PPy, hydrous MnO2 , and MnO2 /PPy nanocomposite electrodes in supercapacitor structure.

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stant current density 2 mA cm2 . The data are plotted in Fig. 7. It shows that the supercapacitor made from pure MnO2 electrodes have a much smaller capacitance, but a relatively stable specic capacitance up to 5000 redox cycles. The supercapacitor formed with PPy electrodes when subjected to same redox cycling, showed initial capacitance of 120 F g1 which degrades by 50% in the rst 1000 cycles. However, the supercapacitor based on two identical MnO2 /PPy nanocomposite electrodes initially give a much higher specic capacity 180 F g1 and later when subjected to chargedischarge cycling test under similar conditions showed a relatively stable performance degrading only by 10% in the initial 1000 cycles and a relatively stable performance at much higher specic capacity is seen for the subsequent 4000 cycles. It seems the initial 10% decline may be attributed to the loss of unstable MnO2 nanoparticles by dissolution in the electrolyte solution [36]. 4. Conclusion Synthesis and properties of the MnO2 embedded PPy nanocomposite as an electrode material for application in the electrochemical supercapacitor are studied. The MnO2 and PPy electrochemical co-deposition is shown as a viable technique that improves the redox performance of the nanocomposite material signicantly exceeding that of its constituents. PPy was used as support for the nanocrystalline MnO2 to grow as a large surface area material whereas in turn the MnO2 complemented PPy by improving the chain structure, conductivity and stability. Thus formed MnO2 /PPy nanocomposite has exhibited high capacitance (620 C g1 ) and long redox cycling life. Acknowledgement We gratefully acknowledge the nancial support for this research provided by the Ofce of Naval Research (Program Manager, Dr. Paul Armistead) under the ONR contract N00014-031-0195. References
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