Bioelectrochemistry 79 (2010) 261264

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Bioelectrochemistry
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / b i o e l e c h e m

Short communication

Performance of microbial fuel cells with and without Naon solution as cathode binding agent
Yuelong Huang a, Zhen He b, Florian Mansfeld a,
a Corrosion and Environmental Effects Laboratory (CEEL), The Mork Family Department of Chemical Engineering and Materials Science, University of Southern California, Los Angeles, CA 90089-0241, USA b Department of Civil Engineering and Mechanics, University of WisconsinMilwaukee, Milwaukee, WI 53211, USA

a r t i c l e

i n f o

a b s t r a c t
The performance of tubular microbial fuel cells (MFC) with and without Naon solution as binding agent for the cathode catalyst preparation was investigated using different electrochemical techniques. The current output of both types of MFCs was monitored as a function of time using an external resistor. The current did not change much with time and was higher for the water cell (WC) than for the Naon cell (NC). Cell voltage (Uc) current (I) curves were recorded using a potentiodynamic technique. From the UcI curves power concentration (P)I and PUc curves were constructed. The water cell (without Naon) also achieved a higher maximum power output. The internal resistance that was determined from the cell voltage at which the power concentration reached its maximum value was higher for the NC than that for the WC, possibly due to the higher cathodic polarization resistance of the NC cell. The impedance for the cathodes decreased with exposure time for both cells due to increased porosity of the surface layers covering the cathode materials. No changes of the impedance were observed for the WC anode. For the NC anode the impedance spectra changed from a one-time constant system to a two-time constant system at the longer exposure time. 2010 Elsevier B.V. All rights reserved.

Article history: Received 30 November 2009 Received in revised form 24 March 2010 Accepted 25 March 2010 Available online 31 March 2010 Keywords: Microbial fuel cell (MFC) Naon Electrochemical impedance spectroscopy (EIS) Internal resistance Electricity production

1. Introduction Microbial fuel cells (MFC) are bio-electrochemical devices that convert organic materials into electricity using microorganisms as biocatalysts [14]. Bacteria have been identied to be capable of generating electricity from the anaerobic oxidation of organic matter [15]. Several factors have been identied as limiting the power production of MFCs [6], including (1) fuel oxidation at the anode, (2) electron transfer from microbial cells to the anode, (3) ohmic resistance of the circuit, (4) proton transfer through the membrane, and (5) rate of oxygen reduction at the cathode. The method of assembling membrane electrodes can signicantly affect the MFC performance. Many efforts have been made to apply Pt as a catalyst to improve the oxygen reduction rate at the cathode. Naon solution, which is a peruroinated ion-exchange solution, is often used as a binding agent to connect the Pt particles, membrane, and carbon electrode [2,7,8]. A widely used method is that Pt/C powder is mixed with Naon solution to form a paste, which is then applied by brushing, spraying or dipping onto an ion-exchange membrane [7,8]. Employing binding agents is costly and may increase the polarization resistance of the cathode. It would be of great interest

to understand the effect of cathode binding agents on the power output of a MFC in more detail. In this study, a Naon solution was used as a model cathode binding agent. The electricity production from two MFCs with and without Naon solution as cathode binding agent was investigated. Electrochemical impedance spectroscopy (EIS) was employed to characterize the electrochemical properties of the anode and the cathode and provide information concerning the polarization resistances of the anode and cathode electrodes. Currenttime curves were recorded as a function of exposure time using an external resistor. Cell voltagecurrent curves were determined using a potentiodynamic technique. From these curves power concentrationcurrent concentration and power concentrationcell voltage curves were calculated for the water cell (WC) and the Naon cell (NC). 2. Experimental approach 2.1. MFC conguration and operation A schematic and a photograph of the laboratory prototype MFC are shown in Fig. 1. The MFCs were made of a tubular cation exchange membrane (CMI-7000, Membrane International Inc., NJ, USA), which had a diameter of 4.8 cm and a length of 14 cm. The total volume was about 250 cm3 and the liquid volume was 150 cm3. The anode that was placed inside the membrane consisted of carbon granules. It was connected to the external circuit by two titanium wires. The cathode

Corresponding author. Tel.: + 1 213 740 3016; fax: + 1 213 740 7797. E-mail address: mansfeld@usc.edu (F. Mansfeld). 1567-5394/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.bioelechem.2010.03.009

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with the cathode acting as counter electrode (CE) followed by recording of the spectrum for the cathode with the anode serving as CE. 3. Results and discussion Fig. 2 shows an example of the currenttime curves that were recorded over extended time periods. The current did not change much with time and the WC produced higher current values than the NC. The performance of the NC and the WC was investigated by the recording UcI curves. Since the area of the anode was not known, the experimental current and power values were normalized by the liquid volume of the anode compartment which was 150 cm3. Fig. 3 gives a comparison of the current concentration and the power concentration produced by the WC and the NC. Fig. 3a shows the current concentration as a function of the cell voltage for the two cells. The maximum current concentration obtained from the WC (26 A/cm3) was more than twice that from the NC (12 A/cm3) (Fig. 3a). Fig. 3b shows the power concentration as a function of the current concentration. The maximum power concentration produced by the WC was about 1.8 W/cm3 compared to 1.2 W/cm3 for the NC. The maximum power concentration was obtained at a cell voltage of about 200 mV in both cases as can be seen from the PUc curves in Fig. 3c. At the cell voltage Umax where maximum power output Pmax occurs Rint = Rext, where Rint is the internal resistance of the MFC and Rext is the external resistor that is placed between the anode and the cathode to obtain Umax [9]. Rint has been dened as [9]: Rint = Rp + Rp + R ;
a c

Fig. 1. A schematic diagram (a) and photograph of MFC (b).

was a layer of a carbon/Pt mixture that was applied on the outside of the membrane. The carbon/Pt mixture was prepared by two different methods: 1) carbon powder containing 10% of Pt (Vulcan XC 72, BASF Fuel Cell, Inc., NJ, USA) was mixed with the Naon solution (Dupont, Naon peruorinated ion-exchange resin, 1 L for every 1 mg of Pt/C powder) and 2) the Naon solution was replaced by tap water. After the mixture was applied to the membrane, Ni-coated carbon bers (TenaX-J, Toho Tenax Co., Ltd., grade HTS 40, Irvine, CA, USA) serving as current collectors and part of the cathode were wrapped around the membrane and air-dried at room temperature overnight. An Ag/AgCl reference electrode was placed in the anode chamber of each MFC. Both MFCs were fed continuously with a solution containing NaC2H3O23H2O (3 g/L); yeast extract (0.2 g/L); NH4Cl (1 g/L); MgSO4 (0.25 g/L); NaCl (0.5 g/L); CaCl2 (15 mg/L); trace solution (1 mL/L) [3] and phosphate buffered nutrient medium (100 mL/L) containing NaH2PO4 (50 g/L) and Na2HPO4 (107 g/L). The hydraulic retention time was 8 h. Twenty ml of a mixture of anaerobic and aerobic sludge (50/50), which were collected from a wastewater treatment plant (Joint Water Pollution Plant, Los Angeles, CA), was injected into the anode chamber as inoculum. All tests were conducted at room temperature (23 C25 C). 2.2. Data collection The voltage across a Rext = 500 external resistor was recorded every 30 s using a computer based data acquisition system (Keithley 2700 multimeter). These measurements were only interrupted when impedance spectra or cell voltagecurrent curves were recorded. Cell voltage (Uc)current (I) curves were collected by applying a potentiodynamic scan at a scan rate of 0.1 mV/s from the open-circuit cell voltage Uoc to zero cell voltage Uo using a Gamry reference 600 potentiostat. The power concentration P (W/cm3) based on the liquid volume of the MFC was calculated from the UcI curves and plotted as a function of current concentration (j) or cell voltage. The impedance spectra were collected at the open-circuit potential (OCP) of the anode and the cathode using a Gamry reference 600 potentiostat (Garmry instruments, Warminster, PA, USA). An ac voltage signal of 10 mV was applied in a frequency range from 100 kHz to 5 mHz. EIS measurements were conducted by rst recording the impedance spectrum of the anode

a c where Rp and Rp are the polarization resistance of the anode and the cathode, respectively and R contains the ohmic contributions such as the solution resistance between the anode and the cathode, the membrane resistance and the electrical resistance of the electrodes, leads, etc. Rint of the WC was calculated as 117 , while for the NC a value of 195 was obtained. As discussed previously, Rint depends on cell voltage [9]. The impedance spectra obtained for the NC and the WC at the open-circuit potential (OCP) for the cathode and the anode during the exposure times of 120 and 140 days are shown in Fig. 4 as Bode-plots in which the logarithm of the impedance modulus |Z| is plotted vs. the logarithm of the applied frequency f. The impedance spectra of the NC and the WC cell cathodes are in general agreement with the coating model proposed by Mansfeld et al. [10,11] for the analysis of impedance data for polymer coated metals. The decrease of the impedance of the cathode for both MFCs with the exposure time is considered to be due to a decrease of the thickness of the polymer

Fig. 2. Currenttime curves for the WC and the NC (Rext = 500 ) for an exposure time of 34 days.

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Fig. 4. Bode-plots for the cathode (a) and the anode (b) of the WC and the NC for an exposure time of 65 days.

explained at present, however they point to a complex interaction between the anode and the cathode for the NC.

4. Summary and conclusions The performance of tubular MFCs (Fig. 1) with and without Naon solution as a binding agent was investigated using different electrochemical techniques. The currenttime curves (Fig. 2) and the power concentrationcurrent concentration or power concentrationcell voltage curves that were obtained from the experimental cell voltage current curves (Fig. 3) have demonstrated that the power production by the water cell is higher than that of the Naon cell. The internal resistance determined from the power densitycell voltage curves (Fig. 3c) was higher for the Naon cell. The impedance spectra for the cathodes of the two MFCs suggest that this higher value is due to the higher polarization resistance of the Naon cell cathode. The ohmic contribution to the internal resistance (Eq. (1)) was very small (Fig. 4). The Naon polymer layers covering the cathode material (Pt particles and Ni-coated carbon bers) apparently block access of oxygen and thereby reduce the rate of oxygen reduction.

Fig. 3. Cell voltagecurrent concentration (a), power concentrationcurrent concentration (b) and power concentrationcell voltage curves (c) for the WC and the NC for an exposure time of 55 days.

layers covering the graphite bers (increase of high-frequency capacitance) and increased porosity of these layers (decrease of pore resistance at intermediate frequencies) (Fig. 4b). The impedance of the cathode for the NC is higher than that for the WC for both exposure times due to the polymer layers formed during treatment with the Naon solution. The impedance spectra for the WC anode did not change signicantly with time indicating stable behavior (Fig. 4a). The impedance for f b 104 Hz is due to the solution resistance and is very low. The impedance for f b 1 Hz is due to the capacitance of the anode. The impedance spectra for the NC anode at 120 days were different from those of the WC at the same exposure time with a signicantly lower capacitance value. The spectra changed to a two-time constant system for an exposure time of 140 days. These changes cannot be

Acknowledgment The authors acknowledge nancial support from the Chevron Corporation.

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Y. Huang et al. / Bioelectrochemistry 79 (2010) 261264 [6] G.C. Gil, I.S. Chang, B.H. Kim, M. Kim, J.K. Jang, H.S. Park, H.J. Kim, Operational parameters affecting the performance of a mediator-less microbial fuel cell, Biosens. Bioelectron. 18 (2003) 327334. [7] J.R. Kim, G.C. Premier, F.R. Hawkes, R.M. Dinsdals, A.J. Guwy, Development of a tubular microbial fuel cell (MFC) employing a membrane electrode assembly cathode, J. Power Sources 187 (2009) 393399. [8] S. Cheng, H. Liu, B.E. Logan, Increased performance of single-chamber microbial fuel cells using an improved cathode structure, Electrochem. Commun. 8 (2006) 489494. [9] A.K. Manohar, O. Bretschger, K.H. Nealson, F. Mansfeld, The use of electrochemical impedance spectroscopy (EIS) in the evaluation of the electrochemical properties of a microbial fuel cell, Bioelectrochemistry 72 (2008) 149154. [10] F. Mansfeld, Use of electrochemical impedance spectroscopy for the study of corrosion protection by polymer coatings, J Appl. Electrochem. 25 (1995) 187202. [11] F. Mansfeld, L.T. Han, C.C. Lee, G. Zhang, Evaluation of corrosion protection by polymer coatings with electrochemical impedance spectroscopy and noise analysis, Electrochim. Acta 43 (1998) 29332945.

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