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Optimization of Naon content in Naonepolyaniline nano-composite modied cathodes for PEMFC application
Mohammad Zhiani a,*, Hussein Gharibi b, Karim Kakaei b
a b

Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran Department of Physical Chemistry, Faculty of Science, Tarbiat Modares University, Tehran, Iran

article info
Article history: Received 2 August 2009 Received in revised form 13 March 2010 Accepted 5 April 2010 Available online 14 May 2010 Keywords: NaonePANI nano-composite Naon loading optimization Modied cathode ORR PEMFC

abstract
In this research several NaonePolyaniline nano-composite modied cathodes have been fabricated and evaluated in oxygen reduction reaction (ORR) in order to use in proton exchange membrane fuel cell (PEMFC). Modied cathodes made by the wide range of Naon content (from 0 to 1.6 mg cm2) and investigated in the acidic solution by different electrochemical techniques at 25  C. The results indicate the activity of the modied electrodes is increased by employing of NaonePolyaniline nano-composite in the reaction layer, but there is an optimum value for Naon content in the catalyst layer. The modied electrode impregnated by 0.4 mg cm2 of Naon shows the highest activity. Analysis of the surface morphology of the Naonepolyaniline modied electrodes by scanning electron microscopy and electrochemical data reveal that the existence of polyaniline (PANI) nanobers in the catalyst layer before adding Naon solution, improves the homogeneity distribution of the ionomer in catalyst layer, change the morphology of electrode and increase the performance of gas diffusion electrodes (GDEs) in oxygen reduction reaction. 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

The future commercial applications of PEMFCs critically depend on efcient utilization of the platinum catalyst [1,2]. Up to now platinum is the most common catalyst in PEMFCs. The performance of cathode catalyst layer in a PEMFC has a signicant impact on the overall performance of the cell. At a given catalyst loading, the performance of the catalyst layer depends on several factors such as; uniform distribution of catalyst nano-particles and electrolyte chains in the catalyst layer, its microstructure and electron and proton connections between agglomerations in the catalyst layer. Many researchers have been demonstrated the rate of ORR on Pt, is considerably less than hydrogen oxidation reaction (HOR) on Pt. Therefore, enhancement of cathode catalyst activity has been one of the major focuses in development of PEMFC electrodes. Recently many studies have been also

focused on employing of non-precious group metal in cathode in order to cost reduction of whole cell [3,4]. Major breakthroughs in this area have been made by increasing of cathode catalyst activity and reducing of catalyst loading [5,6]. It means catalyst utilization enhancement. Improvement of catalyst utilization not only increases the whole cell performance, but also reduces the cost of the whole system. In order to enhancement of cathode catalyst utilization, the pathways for electron, proton, and oxygen transport must be all provided. There are different approaches for increasing of catalyst utilization; one very successful method is to employ catalyst supported especially carbon-supported Pt catalyst (Pt/C). The ideal support should possess high chemical/electrochemical stability, high electron conductivity, an optimum surface area, and a suitable pore size distribution [7]. Up to now, carbon Vulcan XC72 (Cabot) is the most common support for the

* Corresponding author. Tel./fax: 98 311 3913263. E-mail address: m_zhiani@cc.iut.ac.ir (M. Zhiani). 0360-3199/$ e see front matter 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2010.04.019

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anode and cathode catalysts in PEMFCs. Whilst carbon is an excellent electron conductor, it is a very poor proton conductor mainly due to its hydrophilicity. Pickup et al. explored the effect of increasing the hydrophilicity of the carbon support [8]. Their results showed that the treated catalysts by nitric acid (pre- or post-) have higher performance than the untreated catalyst. It was attributed to improvement of proton conductivity in the catalyst layer, most likely due to the formation of surface carboxylic acid groups. Another approach is deposition of Pt particles only in the electroactive areas of the electrode. This can be done by the sputter deposition of thin layer of catalyst on the surface of electrode or membrane. Many studies have employed sputter deposition technique to localize Pt catalyst at the front surface of the electrode or even directly onto the membrane surface. Srinivasan et al. applied a 50 nm thick layer of Pt to an uncatalyzed gas diffusion layer by sputter deposition, and achieved a tenfold reduction in Pt loading (from 4 to 0.4 mg cm2) without any performance lost [9]. Hirano et al. subsequently showed that the performance of electrodes prepared by sputter deposition with a Pt loading of 0.1 mg cm2 was the same as those prepared using standard materials (Pt/C) at a 0.4 mg cm2 of Pt loading [10]. Cha and Lee further reduced the Pt loading to 0.04 mg cm2 by alternating sputter-deposited Pt layers and painted Naon/carbon-ink layers, with successively lower amounts of Pt in each layer [11]. This technique leads to a very efcient utilization of Pt. Sputter deposition is promising for fuel cells since it results in a larger percentage of Pt being electrochemically active. It also allows very thin active layers fabrication and decrease ohmic and mass-transport overpotentials in the catalyst layer. Sputter deposition is a well established industrial technique in areas such as thin lms and integrated circuits [12], and hence it is anticipated that this technique could be readily adapted to micro fuel cell applications. Another method for catalyst utilization improvement is to add a proton-conducting polymer (such as Naon) into the catalyst layer. Pt catalyst near to or directly in contact with membrane is utilized most efcient and decreased with depth of the catalyst layer, largely due to its limited proton conductivity. Naon solution can be applied onto preformed electrodes or directly mixed with the catalyst during ink preparation [12e16] in order to increase the proton conductivity of the catalyst layer. In 1986, Raistri was able to demonstrate that a Pt/C catalyst mixed with Naon could outperform conventional Pt black electrodes that had a tenfold-higher Pt loading [17]. This represented a major breakthrough in fuel cell development by signicantly reducing the required Pt and the cost as well. When designing an electrode using carbon-supported catalyst and Naon, these constituents must be mixed in proportions that result in a stable three-phase boundary where the gas, ion conductor, and catalytically active electron-conducting phase are all present. This requirement limits the amount of Naon that can be added, since its morphology, low gas permeability, and low electron conductivity disrupts this boundary and adversely affects electrode performance [18,19]. This plus the high cost of Naon have prompted investigations into alternative methods and materials for providing high proton and electron conductivity in the catalyst layer [20,21].

Introduction of electroneproton conductive polymers such as polyaniline doped with triuoromethanesulfonic acid as a proton-conducting monomer [22], or a hybrid material such as PANIeNaon composite in the catalyst layer [23], are new promising methods for resolving the problems outlined above. Such materials frequently manifest properties that cannot be achieved by using the components individually; this is particularly true when one of the components is present in a nano-dimensional phase. These compounds exhibit useful physiochemical properties in addition to chemical stability, opening up possibilities for their use in many types of electrochemical devices, including batteries and fuel cells [24]. Pei Kang Shen et al. [25] investigated the thermal properties, absorbance, proton conductivity and cell performance of the Naonepolyaniline composite membrane by different techniques. Their results showed that the proton conductivity of the composite membrane was superior compare to the Naon112 membrane at low humidity. They supposed the existence of the conjugated bonds in the polyaniline facilitate proton transfer and electronic conductivity at the membraneelectrode interface, i.e. the proton transfer via the conjugated bonds at lower humidity retaining high conductivities. At the same time, Kannan et al. [26] made new membrane-electrode assembly (MEA) conguration with doped PANI based interlayer between the catalyst layer and micro-porous layer of the GDL and evaluated in PEMFC at lower RH conditions. They found all the doped PANI interlayer based MEAs exhibited enhanced fuel cell performance at low RH conditions due to improved water management. The improved water management was attributed to the balanced hydrophilicity of the interlayer. The aromatic backbone of the conducting doped PANI provides the hydrophobicity and the functionalization by the dopants provides the sites for water transport by hydrogen bonding. The inuence of the oxidation state of the polyaniline on physicochemical and transport properties of the Naonepolyaniline composite membrane have been also studied by Won Hi Hong et al. [27]. Their results showed in particular, Naon-doped Emeraldine salt (PANI-protonated form) membranes exhibited a higher selectivity and superior cell performance in direct methanol fuel cell (DMFC) compared to those of other oxidation states. They found the morphology and physicochemical properties of composite membranes were controlled by specically manipulating the interactions between Naon and PANIs by means of the oxidation states of PANI. These ndings provide a deeper understanding of the inuence of the PANI oxidation states on the PANIeNaon composite materials and their physical and chemical properties. There are also many other studies that clearly demonstrated that the PANIeNaon based MEAs effectively reduce methanol crossover and perform well when DMFC operated at elevated methanol concentrations, which is highly desirable for portable application [28,29]. Although new promising results have been recently achieved by employing PANIeNaon composite in PEMFC or DMFC but, much more studies on the electrode and MEA making, cell performing conditions, materials durability and their degradation factors need to carry out for fully evaluating of such hybrid materials in PEMFCs or DMFCs. In our previous published works, we compared the activity of the PANI modied electrode and PANIeNaon modied

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electrode with conventional Naon modied electrode as cathode in ORR [22,23]. In both case, results indicated the catalytic activity of electrodes increased considerably when PANI was introduced into the catalyst layer but, the ratio of Naon and PANI in the Naon-PANI composite did not optimized. In the present study, rst the catalyst layer of the identical GDEs was modied with PANI nanobers then, PANI modied electrode impregnated by different amount of Naon loading. The Naon loading of the PANI modied GDEs has been optimized by employing different electrochemical techniques. Finally the morphology of modied electrodes has been studied by scanning electron microscopy (SEM) technique.

2.
2.1.

Experimental
Fabrication of Naon-PANI modied cathode

roughness factor (RF) of the electrodes catalyst layer. The modied electrodes were evaluated at ORR in the acidic solution containing 0.5 M of H2SO4. All measurements were carried out at 25  C in a conventional three-electrode cell conguration. The GDEs were mounted in a glass holder containing a Pt disk as the current collector and with provision for oxygen feeding from the back of the electrode at the ow of 50 ml/min. A large-area Pt at electrode was used as a counter electrode. An Ag/AgCl reference electrode was placed close to the surface of the working electrode. The geometric surface area of electrodes was 2.4 cm2. The electrochemical cell was connected to the potentiostategalvansotat instrument in order to obtain IeV polarization curves and cyclic voltammograms. A frequency response analyzer (model 1025) has been employed for electrochemical impedance spectroscopy (EIS) measurements. The AC potential amplitude was 5 mV and the frequency was scanned between 100 kHz and 0.1 HZ.

The process of electrodes fabrication and modication comprised three steps: (1) construction of the polytetrauoroethylene (PTFE)-bonded porous GDEs, (2) modication of the GDEs using PANI doped with triuoromethanesulfonic acid, and (3) impregnation of the PANI modied GDEs by solubilized Naon solution (5%, Aldrich Chemicals) at different loadings. To prepare the PTFE-bonded porous GDE, commercially available electrocatalyst (20% Pt/C powder, Electrochem) and 30% PTFE emulsion were used as described previously [22]. The amount of PTFE in the catalyst layer was 30 wt%, and the Pt loading was 0.2 mg cm2. Finally, the GDEs were modied with a conductive polymer by the electrochemical polymerization of aniline (Merck) and triuoromethanesulfonic acid (Merck). The electrode substrate was placed as a working electrode together with a counter electrode in an electrolytic cell containing an electrolytic polymerization solution consisting of 0.1 M aniline and 0.2 M triuoromethanesulfonic acid. The PANI modied GDEs were produced according to the procedure which described previously [22,23] by employing a potentiostategalvansotat instrument (model 273A, EG&G Princeton Applied Research). This procedure resulted in a thin lm with triuoromethanesulfonic acid retained within the PANI network on the surface of the catalyst layer. Naon solution (5%; Aldrich) was introduced to the electrode by brushing of it on the surface of the PANI modied GDEs. The amount of Naon was varied from 0 to 1.6 mg cm2 as listed in Table 1.

2.3.

SEM characterization

The surface morphology of all modied GDEs was investigated by SEM (model XL 30, Philips).

3.
3.1.

Results and discussion

Electrochemical activity test

CV was used to determine how ESA and Pt utilization percentage varied with the Naon content. Fig. 1 shows the cyclic voltammograms of modied GDEs in the solution containing 0.5 M of H2SO4, where each electrode had a Pt loading of 0.2 mg cm2 with an equal content of PANI and different amount of Naon loading in catalyst layer. The ESA, RF and percentage Pt utilization were calculated from the columbic charge of the hydrogen desorption of each electrode [30]. Table 2 indicates all three parameters; ESA, RF and Pt utilization, increase with increasing of the Naon content,

90 70 50 30 10

I(mA/cm2)

-10 -30 -50 -70 -90

0.0 mg/cm2 nafion

2.2.

Electrochemical measurements

0.3 mg/cm2 nafion 0.4 mg/cm2 nafion 0.5 mg/cm2 nafion

Cyclic voltammetry (CV) was performed to determine the electrochemical surface area (ESA), Pt utilization, and

0.9 mg/cm2 nafion

-110 -130 -150 -500

1.2 mg/cm2 nafion

1.6 mg/cm2 nafion

Table 1 e Naon loading in the NaonePolyaniline nanocomposite modied cathodes. Electrode

Naon content (mg cm2)

-300

-100

100

300

500

700

900

1100

E(mV) vs. Ag/AgCl

GDE1 GDE2 GDE3 GDE4 GDE5 GDE6 GDE7

0 0.3 0.4 0.5 0.9 1.2 1.6

Fig. 1 e Cyclic voltammograms of the Naon-PANI nanocomposite modied cathodes in the potential range of 1.1 to L0.4 V vs. Ag/AgCl by the scan rate of 50 mV/s in the solution containing of 0.5 M H2SO4 at 25  C.

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Table 2 e ESA, RF, and Pt utilization of the Naon-PANI nano-composite Modied Cathodes measured by CV at 25  C in solution containing of 0.5 M H2SO4, Pt loading: 0.2 mg cmL2. Electrode
GDE1 GDE2 GDE3 GDE4 GDE5 GDE6 GDE7

E E0 b log i Ri E0 Er b log i0

(1) (2)

ESA (cm2)
422 434 448 382 356 342 311

RF
176 181 187 159 148 142 130

Pt utilization%
70.3 72.4 74.7 63.7 59.3 57 52

reach to a maximum value of the Naon loading (0.4 mg cm2) and then decrease with further increasing of Naon content. At 0.4 mg cm2 of the Naon loading RF and Pt utilization are 187 and 74.7% respectively. IeV characteristics of the modied electrodes are presented in Fig. 2. This gure indicates the electrodes performance increases considerably by increasing of Naon content from 0 to 0.4 mg cm2, but by further increasing of Naon loading to 1.6 mg cm2, the electrodes performance is deteriorated. At low Naon loading, the electrodes exhibit low electrolytic conductivity, which accounts for their poor performance. The performance of modied electrodes increases with increasing the Naon content, but for a high Naon content a thicker layer of polymer forms inside the pores of the GDE, which introduces mass-transport problems either by retarding the access of gas to the active sites or by ooding the electrode. Analysis of the CV and IeV results show the electrode containing 0.4 mg cm2 Naon exhibits the highest performance in the ORR. The improved performance in the presence of an optimal amount of Naon is attributed to increase in the three-dimensional reaction zone and optimal electron and proton conductivity of the catalyst layer due to the presence of homogeneously dispersed PANI and Naon.

3.2.

Determination of kinetics parameters

The experimental polarization data were analyzed using the following semi-empirical equation proposed by Srinivasan et al. [31]:
900
0.0 mg/cm 2 nafion

700

0.3 mg/cm 2 nafion

0.4mg/cm 2 nafion

where E0 and Er are the open-circuit potential and reversible potential of the electrode respectively, b is the Tafel slope, i and i0 are the current density and exchange current density of the catalyst in ORR respectively. R represents the total contributions of the polarization components, which include the charge-transfer resistance (Rct), the electrolyte resistance (Re), and the mass transfer resistance (Rd) due to the gas crossing through the diffusion and catalyst layers. The mentioned equation was tted to the experimental data by a nonlinear least-squares method [18] and derived kinetic parameters are listed in Table 3. As it has been indicated in Table 3, kinetic parameters vary with varying of Naon loading. In particular, the Tafel slope and total resistance greatly increase with increasing of Naon content. The Tafel slope values changed from 62 to 176 mV/ dec. These changes imply the inuence of different ratedetermining steps for the ORR as a function of Naon loading. Previously, a Tafel slope of 60 mV/dec has been explained by a mechanism of oxygen reduction, where the reaction involves an initial fast charge-transfer step followed by a chemical step, which is the rate-determining step under Longmuir conditions [32]. The reduction in R with increasing of Naon content in the catalyst layer from 0 up to 4 mg cm2 (Table 3) can be explained by increasing of ionic conductivity and extension of gaseelectrolyteeelectrode tree phase boundaries. An increase in R from 0.5 to 1.6 mg cm2 is indicative of reduced active area and/or an increase in the electrolyte resistance. Both phenomena are related to the non-optimized Naon content in the cathode catalyst layer, being insufcient electrolytic conductivity inside the catalyst layer, leading to a low Pt utilization and a high resistance of electrode. The oscillation in E0 of electrode by changing of Naon content could be related to the inuence of Naon content on the activation behavior of the catalyst as reported by other researchers [33,34]. The electrode containing 0.4 mg cm2 of Naon content shows the best performance (i.e. lowest overpotential) by minimizing of the Ohmic resistance, charge-transfer and mass-transport limitations. To maximize the electrode utilization, it is necessary to prepare an environment with a triple interface comprising a PANIeNaon composite, Pt and oxygen. These results also indicate the Naon content has an important effect on the

E (mV) vs. Ag/AgCl

500

0.5 mg/cm 2 nafion

0.9 mg/cm 2 nafion

300

1.2mg/cm 2 nafion

1.6mg/cm 2 nafion

100

-100

Table 3 e Kinetics parameters of Naon-PANI modied cathodes in ORR at 25  C in the solution containing of 0.5 M H2SO4, Pt loading: 0.2 mg cmL2. Electrode
0 20 40 60 80 100 120

E0 (mV)
746 851 841 772 745 786 830

b (mV/dec)
148 117 62 104 149 168 176

Ri (U)
0.889 0.882 0.779 0.927 1.158 1.19 1.311

-300

I(mA/cm2)

Fig. 2 e IeV Polarization curves of the Naon-PANI nanocomposite modied cathodes in the potential range of 0.8 to L0.2 V vs. Ag/AgCl by the scan rate of 50 mV/s in the solution containing of 0.5 M H2SO4 at 25  C.

GDE1 GDE2 GDE3 GDE4 GDE5 GDE6 GDE7

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120

100

-Zimg(mcm-2)

80
0.0 mg/cm 2 nafion

60

0.3 mg/cm 2 nafion

0.4 mg/cm 2 nafion

0.5 mg/cm 2 nafion

40

0.9 mg/cm 2 nafion

1.2 mg/cm 2 nafion

20

1.6 mg/cm 2 nafion

0 0 10 20 30 40 50 60 70

Zrel (mcm-2)
Fig. 3 e Nyquist plots of the Naon-PANI nano-composite modied cathodes at OCV in the solution containing of 0.5 M H2SO4 and 25  C. Fig. 5 e SEM micrograph of the surface of the Naon-PANI modied cathode with Naon loading of 0.3 mg cmL2.

performance of PANI modied electrodes like conventional electrode.

3.3.

AC impedance spectroscopy

EIS is a very powerful technique that yields a vast amount of useful data in a period of short time from a very simple experimental setup. To determine the charge-transfer resistance of the PolyanilineeNaon nano-composite modied cathodes the impedance spectra of electrodes at the open-circuit voltage (OCV) have been recorded. Fig. 3 indicates the Nyquist plots of the modied electrodes at different Naon loading. As it can be understood from Fig. 3, the polarization resistance of the modied electrodes (Rp) becomes minimum value at the Naon loading of 0.4 and 0.5 mg cm2. This result is consistence with the highest IeV performance being observed at the electrode containing 0.4 mg cm2 of Naon.

The correlation of kinetics parameters obtained from IeV curves with RF, Pt utilization obtained from CVs, and OCV impedance spectra has been clearly shown in Fig. 4. By considering Figs. 3 and 4, it could be concluded that at low Naon content, the catalyst particles create a percolating network that assures high electron conduction, whereas the polymer content is too low for high ionic conduction. In this situation the gas can easily reach the reaction sites, but the electrode performance is poor yet due to the low ionic conductivity of the reaction layer, translating to low Pt utilization of electrode. However, by increasing the Naon loading, more than 0.4 or 0.5 mg cm2, the Rp is increased due to the excess polymer cutting off the percolation path of the catalyst particles and hindering gas diffusion in the reaction layer [18]. Therefore mass-transport limitation of oxygen is highlighted at high Naon content. Uchida et al. [35] found that Naon penetrates only into the secondary pores between the agglomerates of the catalyst

200

Impedance (mcm-2), Pt Utilization, Tafel slope (mV/dec), Roughness

180 160 140 120 100 80 60 40 20 0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5 1.6 1.7
Tafel slope (mV/dec)

RF

Utilization -2 Impedance (mcm )

Nafion loading (mg/cm2)

Fig. 4 e Correlation of kinetics parameters of the NaonPANI nano-composite modied cathodes in ORR by RF, percentage Pt utilization and impedance data.

Fig. 6 e SEM micrograph of the surface of the Naon-PANI modied cathode with Naon loading of 0.4 mg cmL2.

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Fig. 7 e SEM micrograph of the surface of the Naon-PANI modied cathode with Naon loading of 0.5 mg cmL2.

Fig. 10 e SEM micrograph of the surface of the Naon-PANI modied cathode with Naon loading of 1.6 mg cmL2.

layer, and increases the catalyst coverage, lls the pores, and decreases the pore volume.

3.4.

SEM characterization

Fig. 8 e SEM micrograph of the surface of the Naon-PANI modied cathode with Naon loading of 0.9 mg cmL2.

Figs. 5e10 show the scanning electron micrographs of PANI modied GDEs which were impregnated by different amount of Naon loadings. At low Naon loading, the porosity of the catalyst layer and hence the pore size are both large enough to ensure the continuous supply of reactants, but by increasing of Naon content, Naon penetrates into the pores between the agglomerates of the catalyst layer, lls the pores, and decreases the porosity and pore volume. These gures also demonstrate the thickness of the PANI nanobers has been increased by increasing of Naon content and conrm the formation of a thin lm of PANI nanobers on the surface of the electrodes. Existence of the PANI nanobers on the surface of the GDEs before adding Naon solution could be supported homogeneous distribution of Naon solution in the reaction layer. PANI nanobers adsorb Naon solution and help better distribution of Naon solution on the surface and across the catalyst layer. This promotes connections between catalyst particles and increases the conductivity and activity of the catalyst layer.

4.

Conclusions

Fig. 9 e SEM micrograph of the surface of the Naon-PANI modied cathode with Naon loading of 1.2 mg cmL2.

In this paper, effect of Naon loading on the performance of the PANIeNaon nano-composite modied cathodes has been investigated in acidic media. The Naon content in the reaction layer of PANI modied electrodes has been optimized by different electrochemical techniques in the solution containing 0.5 M of H2SO4 at 25  C. The optimal Naon content in the Naon-PANI nanocomposite modied cathode obtained 0.4 mg cm2 when the Pt loading was 0.2 mg cm2.

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It has been also found that the existence of homogeneous PANI nanobers before introducing of Naon solution to the electrode, improves homogeneous distribution of Naon solution across the catalyst layer, changes the morphology of electrode, promotes connections between catalyst particles and increases the conductivity and activity of the cathode catalyst layer.

[15]

[16]

[17]

Acknowledgement
The author would like to thanks the support of the Fuel cell Steering Committee and Iranian Nano technology initiative council.
[18]

[19]

references
[20] [1] Song JM, Cha SY, Lee WM. Optimal composition of polymer electrolyte fuel cell electrodes determined by the AC impedance method. J Power Sources 2001;94:78e84. [2] Yoon Y-G, Park G-G, Yang T-H, Han J-N, Lee W-Y, Kim C-S. Effect of pore structure of catalyst layer in a PEMFC on its performance. Int J Hydrogen Energy 2003;28:657e62. [3] Wang Bin. Recent development of non-platinum catalysts for oxygen reduction reaction. J Power Sources 2005;152:1e15. [4] Croy Jason R, Mostafa S, Hickman L, Heinrich H, Roldan Cuenya B. Bimetallic Pt-Metal catalysts for the decomposition of methanol: effect of secondary metal on the oxidation state, activity, and selectivity of Pt. Appl Catal A Gen 2008;350:207e16. [5] Gharibi H, Abdullah Mirzaie R, Shams E, Zhiani M, Khairmand M. Preparation of platinum electrocatalysts using carbon supports for oxygen reduction at a gas-diffusion electrode. J Power Sources 2005;139:61e6. [6] Ticianelli EA, Derouin CR, Srinivasan S. Localization of platinum in low catalyst electrode to attain high power densities in SPE fuelcells. J Electroanal Chem 1988;251: 275e95. [7] Kinoshita K. Carbon: electrochemical and physicochemical properties. New York: Wiley; 1988. [8] Jia NY, Martin RB, Qi Z, Lefebvre MC, Pickup PG. Modication of carbon supported catalysts to improve performance in gas diffusion electrodes. Electrochim Acta 2001;46:2863e9. [9] Srinivasan S, Manko DJ, Koch H, Enayetullah MA, Appleby AJ. Recent advances in solid polymer electrolyte fuel cell technology with low platinum loading electrodes. J Power Sources 1990;29:367. [10] Hirano S, Kim J, Srinivasan S. High-performance protonexchange membrane fuel-cells with sputter-deposited Pt layer electrodes. Electrochim Acta 1997;42:1587. [11] Cha SY, Lee WM. Performance of proton exchange membrane fuel cell electrodes prepared by direct deposition of ultrathin platinum on the membrane surface. J Electrochem Soc 1999;146:4055e60. [12] OHayre R, Lee SJ, Cha SW, Prinz FB. Sharp peak in the performance of sputtered platinum fuel cells at ultra-low platinum loading. J Power Sources 2002;109:483e93. [13] Murphy OJ, Hitchens GD, Manko DJ. High power density proton-exchange membrane fuel cells. J Power Sources 1994; 47:353e68. [14] Poltarzewski Z, Staiti P, Alderucci V, Weiczorek W, Giordano N. Naon distribution in gas diffusion electrodes

[21]

[22]

[23]

[24]

[25]

[26]

[27]

[28]

[29]

[30]

[31]

for solid-polymer-electrolyte-fuel-cell applications. J Electrochem Soc 1992;139:761. Gasteiger HA, Panels JE, Yan SG. Dependence of PEM fuel cell performance on catalyst loading. J Power Sources 2004;127: 162e71. Passalacqua E, Lufrano F, Squadrito G, Patti A, Giorgi L. Naon content in the catalyst layer of polymer electrolyte fuel cells: effects on structure and performance. Electrochim Acta 2001;46:799e805. Raistri ID. In: Van Zee JW, White RE, Kinoshita K, Burney HS, editors. Proceedings of the symposium on diaphragms, separators, and ion-exchange membranes. Pennington, NJ: The Electrochemical Society Inc.; 1986. p. 172. Lee SJ, Mukerjee S, McBreen J, Rho YW, Kho YT, Lee TH. Effects of Naon impregnation on performances of PEMFC electrodes. Electrochim Acta 1998;43:3693. Cheng XL, Yi BL, Han M, Zhang JX, Qiao YG, Yu JR. Investigation of platinum utilization and morphology in catalyst layer of polymer electrolyte fuel cells. J Power Sources 1999;79:75. Yoshida N, Ishisaki T, Watakabe A, Yoshitake M. Characterization of Flemion membranes for PEFC. Electrochim Acta 1998;43:3749e54. Qi Zhigang, Lefebvre Mark C, Pickup Peter G. Electron and proton transport in gas diffusion electrodes containing electronically conductive proton-exchange polymers. J Electroanal Chem 1998;459:9e14. Gharibi H, Zhiani M, Entezami AA, Mirzaie RA, Kheirmand M, Kakaei K. Study of polyaniline doped with triuoromethane sulfonic acid in gas-diffusion electrodes for proton-exchange membrane fuel cells. J Power Sources 2006;155:138e44. Gharibi H, Zhiani M, Mirzaie RA, Kheirmand M, Entezami AA, Kakaei K, et al. Investigation of polyaniline impregnation on the performance of gas diffusion electrode (GDE) in PEMFC using binary of Naon and polyaniline nanobers. J Power Sources 2006;157:703e8. Rajesh B, Ravindranathan Thampi K, Bonard JM, Mathieu HJ, Xanthopoulos N, Viswanathan B. Electronically conducting hybrid material as high performance catalyst support for electrocatalytic application. J Power Sources 2005;141:35e8. Yang Jinyan, Shen Pei Kang, Varcoe John, Wei Zidong. Naon/polyaniline composite membranes specically designed to allow proton exchange membrane fuel cells operation at low humidity. J Power Sources 2009;189:1016e9. Cindrella L, Kannan AM. Membrane electrode assembly with doped polyaniline interlayer for proton exchange membrane fuel cells under low RH conditions. J Power Sources 2009;193: 447e53. Choi Bong Gill, Park Ho Seok, Im Hun Suk, Kim Yo Jin, Hong Won Hi. Inuence of oxidation state of polyaniline on physicochemical and transport properties of Naon/ polyaniline composite membrane for DMFC. J Membr Sci 2008;324:102e10. Wang C-H, Chen C-C, Hsu H-C, Du H-Y, Chen C-P, Hwang J-Y, et al. Low methanol-permeable polyaniline/Naon composite membrane for direct methanol fuel cells. J Power Sources 2009;190:279e84. Neburchilov Vladimir, Martin Jonathan, Wang Haijiang, Zhang Jiujun. A review of polymer electrolyte membranes for direct methanol fuel cells. J Power Sources 2007;169: 221e38. Sasikumar G, Ihm JW, Ryu H. Dependence of optimum Naon content in catalyst layer on platinum loading. J Power Sources 2004;132:11e7. Ticianelli EA, Derouin CR, Redondo A, Srinivasan S. Methods to advance technology of proton exchange membrane fuel cells. J Electrochem Soc 1988;135:2209.

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[32] Antolini E, Giorgi L, Pozio A, Passalacqua E. Inuence of Naon loading in the catalyst layer of gas-diffusion electrodes for PEFC. J Power Sources 1999;77:136e42. [33] Paganin VA, Ticianelli EA, Gonzalez ER. Development and electrochemical studies of gas diffusion electrodes for polymer electrolyte fuel cells. J Appl Electrochem 1996;26:297.

[34] Sasikumar G, Ihm JW, Ryu H. Optimum naon content in PEMFC fuel cell electrodes. Electrochim Acta 2004;50:601e5. [35] Uchida M, Aoyama Y, Eda N, Ohta A. Investigation of the microstructure in the catalyst layer and effects of both peruorosulfonate ionomer and PTFE-loaded carbon on the catalyst layer of polymer electrolyte fuel cells. J Electrochem Soc 1995;142:4143.