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Bioresource Technology
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Article history:
Received 13 June 2011
Received in revised form 15 August 2011
Accepted 18 August 2011
Available online 13 September 2011
Keywords:
Diffusion
Impedance analysis
Oxygen transfer
Olen sheet
PTFE
a b s t r a c t
The power production performance of a membrane-less aircathode microbial fuel cell was evaluated for
53 days. Anode and cathode electrodes and the micro-ber cloth separator were congured by sandwiching the separator between two electrodes. In addition, the air-facing side of the cathode was covered with
a spunbonded olen sheet instead of polytetrauoroethylene (PTFE) coating to control oxygen diffusion
and water loss. The conguration resulted in a low resistance of about 4 X and a maximum power density
of 750 mW/m2. However, as a result of a gradual decrease in the cathode potential, maximum power density decreased to 280 mW/m2. The declining power output was attributed to loss of platinum catalyst
(8.26%) and biomass growth (38.44%) on the cathode. Coulombic efciencies over 55% and no water leakage showed that the spunbonded olen sheet covering the air-facing side of the cathode can be a costeffective alternative to PTFE coating.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
Microbial fuel cells (MFCs) use electrochemically active anaerobic bacteria as biocatalysts to convert chemical energy contained in
the bonds of organic compounds to electrical current, where bacteria derive energy from the oxidation of the substrate (Rabaey and
Verstraete, 2005). In a typical MFC, the anode and the cathode
are separated by a proton exchange membrane (PEM) and are
placed in two separate chambers (Logan et al., 2006). Electrons
produced by the microorganisms from electron donors are transferred to the anode and ow to the cathode by an external circuit.
To compensate for the electron transfer to the cathode, protons
ow from anode to cathode through the bulk liquid and through
the ion selective membrane separating the anode and the cathode
(Logan et al., 2006; Rabaey and Verstraete, 2005). Electrons that
reach to the cathode combine with protons and electron acceptor
(mainly oxygen) to produce water (Bond et al., 2002). In addition
to two-chambered MFCs, it is also possible to design single
-chambered MFCs, which do not require cathode to be placed in
water (aircathode MFC) (Liu and Logan, 2004; Liu et al., 2004).
The single-chambered air cathode offers several advantages over
two-chambered systems such as; (a) the cathode does not need
to be aerated, oxygen in the air can directly react at the electrode,
(b) recycling or chemical regeneration of the catholyte is not required, and (c) higher volumetric power density is easily achiev Corresponding author. Tel.: +90 216 348 0292x289; fax: +90 216 347 4090.
E-mail addresses: evrentugtas@gmail.com (A.E. Tugtas), plncavdar@yahoo. com
(P. Cavdar), baris.calli@marmara.edu.tr (B. Calli).
0960-8524/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2011.08.082
able due to smaller cell volume (Fan et al., 2007; Liu and Logan,
2004; Liu et al., 2004). Aircathode MFCs have shown to produce
higher power output when operated without PEM (membrane-less
MFC), which has been attributed to higher cathode potential (Liu
and Logan, 2004; Liu et al., 2004). However, the major drawback
of a membrane-less air cathode MFC is oxygen diffusion into the
anode, which promotes the consumption of acetate by aerobic bacteria and thus results in lower Coulombic efciency (CE) (Cheng
et al., 2006a; Liu et al., 2004). Oxygen diffusion to anode can be
controlled by applying cathode coatings, such as polytetrauoroethylene (PTFE), which would form hydrophobic gas diffusion layer
on the air side of cathode (Cheng et al., 2006a). PTFE coating on
cathode improves the power density/Coulombic efciency and
has been used as a diffusion layer in most of the air cathode studies
(Cheng et al., 2006a; Nimje et al., 2011; Pant et al., 2010; Wang
et al., 2010). PTFE is a highly hydrophobic material, which is used
to prevent water leakage in MFCs and it has good oxygen transfer
efciency (Cheng et al., 2006b). However, PTFE may limit effective
proton transfer to the catalyst due to its highly hydrophobic nature
(Cheng et al., 2006b). In addition, PTFE is one of the expensive components of MFC. Reducing the total cost of MFC while increasing
the power densities has become signicant in recent years (Li
et al., 2011; Logan, 2009). Pilot or full scale continuous-ow MFC
applications may be available only if low cost and sustainable
materials are used (Logan, 2009). Many studies has offered lowcost alternatives to different parts of MFCs, however, research on
a low-cost alternative to PTFE-diffusion layer is still very limited.
In this study, power generation performance of a membraneless air cathode MFC (MLAC-MFC) fed with acetate containing
10426
2. Methods
2.1. Conguration of MLAC-MFC
MLAC-MFC having a 230 mL cubic anode chamber was made of
transparent acrylic plates (Fig. 1). Commercially available anode
and cathode electrodes each having 36 cm2 surface area
(6 cm 6 cm) were 1.5-mm thick carbon cloth (Clean fuel cell energy, FL, USA, CC, LLC) and the cathode electrode (Clean fuel cell energy, FL, USA, XC-72, LLC) contained 1 mg/cm2 platinum catalyst
coating on the water facing side of the carbon-cloth. Anode and
cathode electrodes were used as supplied by the manufacturer.
Electrodes were physically separated by a 1-mm thick non
-conductive microber cleaning cloth (Scotch-Brite) in preference
to a proton exchange membrane (PEM). Anode and cathode
electrodes and the micro-ber cloth separator were congured as
cloth-electrode assembly (CEA) by sandwiching the separator between two electrodes. Electrodes, the separator, and the spunbonded olen sheet were adjoined to each other only by a
physical contact. Chemical xation was not used. The anode electrode of the MFC was transferred from another acetate-fed MFC,
which had been operated under same anodic conditions as the
one used in this study for over two months. The biolm covered
anode was exposed to air for a considerable amount of time during
the transfer. Therefore, in order to overcome the negative effects of
oxygen exposure and to facilitate rapid establishment of favorable
anodic conditions, the MFC was operated as a half cell on the rst
3 days of the start-up by placing an air/water impermeable layer to
the air facing side of the cathode. Impermeable layer was removed
subsequent to the establishment of negative anode potentials and
a water impermeable spunbonded 100% olen sheet (Tyvek,
Rex
Carbon Cloth Anode
Effluent
Biofilm
CO2
Cloth Separator
Carbon cloth
Cathode
(1 mg/cm2 Pt)
H 2O
Reference Electrode
Acetate
O2
Diffusion Layer
Influent
Magnetic
Stirrer
Dupont, 1060B) was placed on the air facing side of air breathing
cathode as a diffusion layer without disturbing the operation of
the cell. Polyolenic materials are by far the most important class
of synthetic polymers and the polyolens of polyethylene (PE) and
polypropylene (PP) are two of the three most widely used synthetic
polymers in the world (Mitani et al., 2004; Sun et al., 1999). This
lightweight, durable and low cost polyolen sheet was made of
high density polyethylene bers (0.15 mm thickness) and widely
used as house-wrap material. Polyolen sheet has a variable pore
size; however, the pore sizes are smaller than 1 lm. The chemical
and physical characteristics of the polyolen sheet were obtained
from the suppliers technical data sheets and are reported in Table
1. Polyolen is a non-biodegradable material (Zheng et al., 2005),
however to the best of our knowledge, there is no information on
the biodegradability of spunbonded olen sheet, which was used
in this study. An Ag/AgCl reference electrode (Schott Inst.,
+0.197 V according to standard hydrogen electrode, SHE) was located in the anode chamber and connected to the electrodes for
the measurement of anode and cathode potentials (Fig. 1).
2.2. Operation of MLAC-MFC
The anode chamber of MLAC-MFC was continuously fed
(240 mL/d) with synthetic wastewater using a peristaltic pump
(Watson Marlow, 323Du). The hydraulic retention time (HRT)
was about 23 h. The anode compartment was continuously mixed
with a magnetic stirrer (VELP, Multistirrer 6). Anode compartment
was purged with N2 gas in order to establish anaerobic conditions
during the rst few days of the start-up period. The experiment
was carried out in the dark at 25 0.5 C.
2.3. Inoculum and medium
The anode electrode of MLAC-MFC was transferred from another MFC and inoculated in order to compensate for the loss of
biolm from the anode surface during the transfer. Inoculation
was done using the efuent of the same MFC, which was developed
with the sludge obtained from a municipal wastewater treatment
plant (Pasakoy WWTP, Istanbul) and maintained over a year with
sodium acetate as the sole carbon source. The synthetic wastewater was prepared according to previous studies (Rabaey et al.,
2005; Rozendal et al., 2006) and its pH was maintained at about
7.0 using 20 mM phosphate buffer. The carbon source in the synthetic feed was 180 mg/L acetate. Organic loading rate of about
0.2 kg acetate-COD/m3 d was applied. The feed solution was kept
at 5 1 C using a water bath connected to a refrigerated recirculator (LAUDA, RE104).
2.4. Electrochemical monitoring and analytical methods
Cell voltage (mV) was measured on-line every 60 s over a 10-X
current resistor by two 24-bit analog input data acquisition modules (NI, USB9239). The external cell resistance (Rex) comprising
a 10 X current resistance was adjusted to a value between 10 X
and 18.6 kX by using the 16-bit digital relay board connected to a
predened array of resistors. Ag/AgCl reference electrodes
(+0.197 V according to SHE) were connected to the same module.
The potential differences between reference electrodes and operating electrodes were monitored as anodic and cathodic half-cell
potentials. The collected cell voltage, external resistance, anode
and cathode half-cell potential data were transferred to a personal
computer. A computer program was designed using LabVIEW
programming software (Version 8.5) to calculate the current (mA)
and power (mW) and plot their time-based graphs. The current
(I, mA) and power (P, mW) were calculated according to Ohms
Law, and was normalized to the projected surface area (36 cm2)
Method
Unit
Mean Value
2
BS 2782:320A
BS 2782:320A
BS 2782 Method
620A
EN ISO 12572
N/mm
%
g/m2
m
0.01
EN12114
m3/(m2 h
50 Pa)
<2
39.79
14.38
61
No
penetration
a
This information was obtained from DuPONT, Tyvek technical data sheet for
Tyvek 1060 B. Values are reported for unaged polyolen sheets.
of the anode. The Columbic Efciency (CE) was calculated by integrating the measured current relative to the theoretical current
based on the consumed acetate (Logan et al., 2006).
Total solids (TS) and volatile solids (VS) measurements on the
cathode electrode (1 cm2) were conducted at the beginning and
end of the experiment according to procedures described in Standard Methods (American Public Health Association, 1998). Liquid
samples were centrifuged at 2656g for 10 min, and ltered
through 0.45 lm syringe lters. Samples for acetic acid analysis
were diluted with 8 mM sulfuric acid solution and stored at 4 C
until analysis. The samples were analyzed for acetic acid using a
high performance liquid chromatography (HPLC) unit (Shimadzu
Prominence LC-20A), which was equipped with transgenomic ICsep COREGEL-87H3 (7.8 300 mm) column and UV detector
(210 nm). The column compartment temperature was set at
35 C and the injection volume was 20 lL. The eluent used in acetic
acid measurement was 8 mM sulfuric acid solution with a ow rate
of 0.8 mL/min. Cathode electrode was tested for its platinum content before and after the experiment. A fresh and used cathode
electrode was cut in 1 cm2 pieces and digested with 10 mL Aqua
Regia (3:1 HCl:HNO3) using a MARS Microwave (CEM, USA)
equipped with an EasyPrep vessel system. Digestion was carried
out at 180 C with a ramp time of 20 min and a hold time of
25 min. Platinum in digested samples were analyzed using Thermo
X Series ICP-MS coupled with Cetac ACX-510 automatic sampler.
Internal resistance of an MFC at an applied cell voltage can be
determined via impedance measurement, which is conducted by
applying an external source instead of using the current produced
by the MFC (He and Mansfeld, 2009). Electrochemical impedance
spectroscopy (EIS) analysis was used to determine the total internal resistance (RIN) and its components. RIN consists of three components: polarization (RP: charge transfer) resistance, ohmic
resistance (RX: resistances from solution, electrode materials and
membrane) and concentration (diffusion) resistance (He and
Mansfeld, 2009). The internal resistance of MLAC-MFCs was analyzed by using LabVIEW program over a frequency range of
0.0140 Hz between the anode and the cathode. The anode was
used as the working electrode and the cathode was used as the
counter and reference electrode. A small AC signal (10 mV amplitude) was applied during the measurement to stimulate the current response from the MFC without affecting its performance.
Impedance spectra were collected at a constant applied potential
and the results were shown as Nyquist plot. A Nyquist plot expresses the impedance with a real part (ReZ plotted on the X-axis)
and an imaginary part (ImZ plotted on the Y-axis that is negative).
Nyquist plots include a semicircular region lying on the axis followed by a straight line. The semicircular portion corresponds to
a electron transfer limited process and the linear portion represents the diffusion limited portion (Wang, 2006). The intercept of
the curve with the ReZ axis was considered as RX and ReZ value
10427
of the lowest frequency was considered as RIN. The difference between RIN and RX is charge transfer resistance (RP) plus diffusion
resistances (He and Mansfeld, 2009).
Chronoamperometry tests were performed to draw polarization
and power density curves and to evaluate the oxidation/reduction
properties of anode and cathode by feedback-controlling the current obtained between them without the need of a potentiostat.
In CV tests, a 16-bit digital relay board connected to a predened
array of resistors allowed up to 216 (65,536) different resistance
values between 10 X and 18.6 kX. By using the LabView program
developed for feedback-controlling the current, a relatively linear
current scan was achieved. The external resistance was controlled
by a simple feedback loop, which enabled not only the operation at
a desired current set-point but also the programmed stepwise shift
of the current, which allowed a linear current change (e.g. 0.2 mA
in every 5 s) over time. The low scan rate was selected to allow sufcient time for the biolm to interact with the electron accepting
anode electrode.
10428
600
Cell Voltage
POTENTIAL (mV)
400
200
Cathode Potential
0
-200
Anode Potential
-400
-600
0
10 15 20 25 30 35 40 45 50 55
TIME (Days)
Fig. 2. Cell voltage, anode and cathode potentials of MLAC-MFC (180 mg/L acetate,
and 150 X external resistance).
100
ACETATE REMOVAL
EFFICIENCY (%)
80
60
40
20
0
100
B
COULOMBIC
EFFICIENCY (%)
80
60
40
20
0
0
5 10 15 20 25 30 35 40 45 50 55
TIME (Days)
Fig. 3. Acetate removal efciency (A) and coulombic efciency (B) of MLAC-MFC
operated in continuous ow mode.
10429
300
Day 5
Day 13
POTENTIAL (mV)
200
Day 25
Day 39
Day 6
Day 28
Day 42
100
0
-200
800
RX (X)
RP (X)
130
142
160
4.4
3.9
3.5
125.6
138.1
156.5
-300
-500
600
400
4. Conclusions
200
0
0
500
80
Day 6
Day 28
Day 42
A spunbonded olen sheet was placed on the cathode of a continuous ow membrane-less aircathode MFC and a maximum
power density of 750 mW/m2 and Coulombic efciency of 55%
were achieved. However, a gradual decrease in power density
was observed with continuous-ow operation and attributed to
loss of platinum catalyst and biomass growth on the cathode.
The spunbonded olen sheet was effective in controlling the oxygen diffusion and water leakage.
Overall, the results of this study revealed that spunbonded olen sheet is a cost-effective alternative to PTFE coating and can be
used as a diffusion layer in aircathode MFCs. However, in order
to realize large scale applications of air cathode MFCs with olen
sheet diffusion layer, further studies are required to achieve constant power densities by preventing catalyst loss and controlling
biolm growth on the surface of the cathode.
Acknowledgements
60
ImZ (Ohm)
RIN (X)
-100
-400
Table 2
RX, RP and RIN values determined from Nyquist plots.
40
20
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0
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60
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ReZ (Ohm)
Fig. 5. Nyquist plots of impedance spectra of MLAC-MFC operated in continuous
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Glossary
CE: coulombic efciency (%)
CEA: cloth-electrode-assembly
DO: dissolved oxygen (mg/L)
EIS: electrochemical impedance spectroscopy
HRT: hydraulic retention time (hour)
Hz: Hertz
I: current (Ampere)
ImZ: imaginary impedance
MLAC-MFC: membrane-less air cathode microbial fuel cell
PEM: proton exchange membrane
ReZ: real impedance
SHE: standard hydrogen electrode
V: voltage (Volt)