ISSN 0012-5016, Doklady Physical Chemistry, 2007, Vol. 415, Part 2, pp. 234236. Pleiades Publishing, Ltd., 2007.

. Original Russian Text A.Yu. Tsivadze, M.R. Tarasevich, B.N. Efremov, N.A. Kapustina, P.V. Mazin, 2007, published in Doklady Akademii Nauk, 2007, Vol. 415, No. 6, pp. 775778.

PHYSICAL CHEMISTRY

A Fuel Cell with a Cation-Exchange Membrane for Direct Oxidation of Ethanol in an Alkaline Medium
Academician A.

Yu. Tsivadze, M. R. Tarasevich, B. N. Efremov, N. A. Kapustina, and P. V. Mazin

Received April 17, 2007

DOI: 10.1134/S001250160708009X

Ethanol is a highly efcient liquid fuel for direct oxidation in low-temperature fuel cells (FCs). This is due to its considerable energy capacity (~8 kW h/kg), nontoxicity, and biological renewability. Until now, however, electrocatalysts that provide sufciently complete oxidation of ethanol to CO2 in acid electrolytes (releasing 12 electrons per C2H5OH molecule) have remained unknown. Usually, the electrode process terminates with the formation of acetaldehyde (2e) or acetic acid (4e) [1, 2]. As was recently shown in some works of our institute, efcient oxidation of ethanol with release of no less than (810)e per ethanol molecule is possible in an alkaline medium if carbon-supported nanosized RuM (M = Ni, Co, Fe) are used as anodic catalysts [3, 4]. Other important problems to be solved to ensure the efciency of ethanol liquid fuel are the use of a cathode catalyst tolerant to ethanol and the choice of an ionexchange membrane with a high electrical conductivity and good separation properties for ethanol. The solution of these problems aimed at the creation of the FC optimal design was the object of this work. The closest analogue of the ethanol FC may be a boron hydride FC. The boron hydride cells were described in the literature [5, 6]. In these cells, the electrolyte is an ion-exchange membrane, for example, of the type of Naon in the Na+ form. The ion transport in the boron hydride FC is due to Na+ transfer, which leads to the formation of an alkali in the cathode compartment of the cell. This approach can be used also in the ethanolair FC. The following reactions proceed on the electrodes of an alcohol FC with oxidation of ethanol in an alkaFrumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, 119991 Russia

line medium: Cathode: 3O2 + 6H2O + 12e 12OH 3H2O

Anode: C2H5OH + 12OH 12e 9H2O + 2CO2 3O2 + C2H5OH 3H2O + 2CO2. According to the stoichiometries of the partial reactions, the maximum number of electrons per ethanol molecule is 12e in this electrochemical system. However, until now, only the number of (810)e has been reached. It also follows from the reaction equations that the water formed on the anode dilutes the alkali and the alkali is concentrated in the cathode active layer due to the water consumption. Figure 1 presents the scheme of the processes proceeding in the operating FC. The reduction of oxygen on the cathode produces OH ions, which interact with Na+ ions traveling through the membrane to form an alkali. It should also be kept in mind that ethanol can penetrate through the membrane into the cathode space (the so-called crossover effect) and negatively affect the performance of the cathode.
A M K

H2O + CO2 C2H5OH + NaOH Na+ NaOH

O2 + H2O

OH

Fig. 1. The scheme of the processes occurring in a direct ethanol fuel cell with a cation-exchange membrane in an alkaline medium. A designates the anode, K stands for the cathode, and M is the membrane.

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A FUEL CELL WITH A CATION-EXCHANGE MEMBRANE FOR DIRECT OXIDATION

235

This is why the requirement for the catalyst tolerance to ethanol arises. Three cathode catalysts were studied, namely, the Pt(20 wt %)/C (the commercial catalyst E-TEK), Pt N4Co (7.3% Pt)/C [7], and N4Co/C [8] catalytic systems supported on XC-72 carbon black. The electrocatalytic activity towards the oxygen reduction and the tolerance to ethanol were studied under model conditions using a rotating disk electrode covered with a thin catalyst layer by the procedure described in [9] in a 1 M KOH solution at 60. The experimental results are presented in Fig. 2 and the table. According to the data obtained, the following activity series was observed in an oxygen atmosphere: Pt/C PtN4Co/C > N4Co/C. The same order of activities was also found for electrooxidation of ethanol. Because of this, the effect of ethanol on the cathode reaction of oxygen reduction occurring by the mechanism of coupling of the anodic and cathodic reactions is the most pronounced for Pt/C and the least pronounced for the N4Co/C system. In case of the Pt/C and Pt N4Co/C systems, the negative effect of ethanol is accompanied by poisoning of Pt-containing catalysts in its presence. As is seen from Fig. 2, this leads to deceleration of the current buildup at the potentials more negative than the potentials of the ethanol oxidation. This is the reason for observing another activity series in the simultaneous presence of O2 and 0.5 M C2H5OH in an alkaline solution, namely, N4Co/C > PtCo/C > Pt/C. Therefore, the N4Co/C system is the most tolerant to ethanol. The commercially available Pt/C E-TEK catalyst and the N4Co/C catalyst were used for formation of cathodes for the direct ethanol fuel cell. The anodes were prepared on the basis of the NiRu(68 : 32)/C system [3]. An ion-exchange membrane made from Naon-117 in the Na+ form was used as a polymeric electrolyte membrane. This choice was made taking into account the large thickness of this membrane (180 m), which should decrease the rate of ethanol transfer to the cathode. The fuel mixture included 2 M C2H5OH and 6 M NaOH solutions. The FC operating temperature was 60. The cathodes and anodes for the membraneelectrode unit 5 cm2 in area were made with the use of a 5% Naon solution. A standard hydrophobic TORAY

I, m/cm2 0.4 0.2 3' 0 0.6 0.7 0.8 0.9 1.0 E, V 1' 2'

1.0 1 2 3 3'' 1''

2.0

Fig. 2. Polarization curves for (13, 1", 3") the oxygen reduction and (1'3') the ethanol oxidation in the presence of oxygen obtained in (1", 3") a 1 M KOH solution and (13, 1'3') in 1 M KOH + 0.5 M C2H5OH on a rotating disk electrode (m = 640 rpm) with a thin layer (120 g/cm2) of a catalyst: (1, 1', 1") Pt/C (E-TEK), (2, 2') PtN4Co(7.3%)/C, and (3, 3', 3") N4Co/C.

(EC-TP1T) carbon paper was used as a current collector and a gas diffusion layer. The active anode layer contained 20 mg/cm2 of 15% RuNi/C. The active cathode layer contained 2 mg/cm2 of the commercial Pt(40%)/C E-TEK catalyst or 4 g/cm2 of pyropolymer of cobalt tetra(methoxyphenyl)porphyrin (N4Co/C). The composition for preparing the active cathode layer included, in addition to a catalyst, bidistilled water, ethanol, and a 5% Naon solution. After an ultrasonic treatment, the homogeneous dispersion obtained was deposited on the TORAY carbon paper layer by layer. Figure 3 shows the currentvoltage curves of the oxygen reduction that were obtained on two cathodes of the membraneelectrode units of the FC. Taking into account the ethanol transfer through the membrane and the tolerances to alcohol of the catalysts under study, these results conrm the conclusions drawn on the basis of the model investigations. Inasmuch as the N4Co/C catalyst is more tolerant to ethanol compared

Characteristics of various cathode systems in 1 M KOH at 60C in an oxygen atmosphere in the presence and absence of 0.5 M C2H5OH O2 Catalyst Est , V 1.02 0.97 0.92 I, mA/cm2 at E = 0.88 V 1.2 0.7 0.26
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O2 + 0.5 M C2H5OH E -------------,V log I 0.060, 0.110 0.060, 0.120 0.050, 0.110
Part 2 2007

Est , V 0.87 0.9 0.91

I, mA/cm2 at E = 0.88 V 0.04 0.087 0.18

C2H5OH (0.5 M), I, mA/cm2 at E = 0.95 V 0.35 0.30 0.039

Pt/C PtN4Co/C N4Co/C

DOKLADY PHYSICAL CHEMISTRY

236 E, mV 1100

TSIVADZE et al. U, mV 1000 P, mW/m2 40

1000 800 1 900 2 800 1 400 700 0 20 40 60 80 I, m/m2 0 20 40 I, m/m2 60 80 600 2 3

30

20

10

Fig. 3. The currentvoltage curves of the oxygen reduction on the (1) N4Co/C and (2) Pt/C catalysts in the FC with direct oxidation of ethanol at 60C.

Fig. 4. (1, 2) The currentvoltage curves and (3) power density curve for the FC with direct oxidation of ethanol at 60C with the (1) Pt/C and (2, 3) N4Co/C catalysts.

with the Pt/C catalyst, the cell current density for the cathode with the nonplatinum catalyst is considerably higher than that for the cathode containing platinum. In order to increase the discharge currents of the FC, the optimization of the contents of the N4Co/C catalyst in the active cathode layer and of the RuNi/C catalyst at the anode was performed. The following results were obtained. A simple increase in the contents of both catalysts does not increase the cell current density because of difculties with removing the alkali from the cathode and feeding ethanol to the anode. For the chosen compositions of the active layers of the electrodes, the maximum currents are observed for the minimum thickness of the cathode and anode, to which the following contents of the catalysts correspond: 45 mg/cm2 of N4Co/C and 20 mg/cm2 of RuNi/C. Thus, under equal other conditions, a better current voltage curve should be observed for the FC with the N4Co/C cathode, which was conrmed experimentally (Fig. 4, curves 1, 2). The power density of this FC (curve 3) was about 40 mW/cm2. Considering that a FC with the direct oxidation of ethanol whose electrodes contain no platinum is described in this work for the rst time, this result may be thought of as quite satisfactory and encouraging. Summarizing the above, we can conclude that the studies performed allowed us to create a new design concept of the ethanolair FC and showed the feasibility of a FC with a cation-exchange membrane for direct ethanol oxidation in an alkaline medium without a Pt catalyst. The result was obtained due to the use of the efcient RuNi/C anodic catalyst and the N4Co/C cathodic catalyst, tolerant to ethanol. The discharge characteristics of this FC can be improved by further

optimization of the membraneelectrode unit and substantiation of more accurate FC operating conditions. ACKNOWLEDGMENTS This work was supported by the national innovation company New Energy Projects and the Foundation for Assistance to Small Enterprises in the Area of Science and Technology. REFERENCES
1. Countaceau, C., Demarconnay, L., Lamy, C., and Leger, J.-M., J. Power Sources, 2006, vol. 156, p. 14. 2. Colmenares, L., Wang, H., Jusys, Z., Jiang, L., Yan, S., Sun, G.Q., and Behm, R.J., Electrochim. Acta, 2006, vol. 52, p. 221. 3. Tarasevich, M.R., Karichev, Z.R., Bogdanovskaya, V.A., Lubnin, E.N., and Kapustin, A.V., Electrochem. Commun., 2005, vol. 7, p. 141. 4. Tarasevich, M.R., Karichev, Z.R., Bogdanovskaya, V.A., Kapustin, A.V., Lubnin, E.N., and Osina, M.A., Elektrokhimiya, 2005, vol. 41, p. 829. 5. Gyenge, E., Atwan M., Northwood D, J. Electrochem. Soc., 2006, vol. 153, p. A150. 6. Cheng, H. and Scott, K., J. Power Sources, 2006, vol. 160, p. 407. 7. Tarasevich, M.R., Bogdanovskaya, V.A., Lubnin, E.N., and Reznikova, L.A., Korroz. Mater. Zashch., 2006, vol. 10, p. 22. 8. Tarasevich, M.R., Radyushkina, K.A., and Zhutaeva, G.V., Elektrokhimiya, 2004, vol. 40, p. 1174. 9. Tarasevich, M.R., Chalykh, A.E., Bogdanovskaya, V.A., Kuznetsova, L.N., Kapustina, N.A., Efremov, B.N., Ehrenburg, M.R., and Reznikova, L.A., Electrochim. Acta, 2005, vol. 51, p. 4455.
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