i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 3 0 9 6 e1 3 1 0 4

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Effects of gas diffusion layer (GDL) and micro porous layer

(MPL) on cathode performance in microbial fuel cells (MFCs)

Carlo Santoro a,c, Alexander Agrios a,c, Ugur Pasaogullari b,c, Baikun Li a,c,*
a
Department of Civil and Environmental Engineering, University of Connecticut, Storrs, CT 06269, USA
b
Department of Mechanical Engineering, University of Connecticut, Storrs, CT 06269, USA
c
Center for Clean Energy Engineering, University of Connecticut, Storrs, CT 06269, USA

article info abstract

Article history: This study focused on novel cathode structures to increase power generation and organic
Received 2 April 2011 substrate removal in microbial fuel cells (MFCs). Three types of cathode structures,
Received in revised form including two-layer (gas diffusion layer (GDL) and catalyst layer (CL)), three-layer (GDL,
1 July 2011 micro porous layer (MPL) and CL), and multi-layer (GDL, CL, carbon based layer (CBL) and
Accepted 10 July 2011 hydrophobic layers) structures were examined and compared in single-chamber MFCs
Available online 10 August 2011 (SCMFCs). The results showed that the three-layer (3L) cathode structures had lower water
loss than other cathodes and had a high power density (501 mW/m2). The MPL in the 3L
Keywords: cathode structure prevented biofilm penetration into the cathode structure, which facili-
Microbial fuel cells tated the oxygen reduction reaction (ORR) at the cathode. The SCMFCs with the 3L cathodes
Micro porous layer (MPL) had a low ohmic resistance (Rohmic: 26e34 U) and a high cathode open circuit potential
Gas diffusion layer (GDL) (OCP: 191 mV). The organic substrate removal efficiency (71e78%) in the SCMFCs with 3L
Cathode structure cathodes was higher than the SCMFCs with two-layer and multi-layer cathodes (49e68%).
This study demonstrated that inserting the MPL between CL and GDL substantially
enhanced the overall electrical conduction, power generation and organic substrate
removal in MFCs by reducing water loss and preventing biofilm infiltration into the cathode
structure.
Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction gained intense attention for generating electricity from

wastewater treatment [1]. An MFC is a bioreactor capable of
Efficient production of clean energy is critical for solving converting chemical energy stored in organic compounds (e.g.
emerging energy shortage and environmental pollution glucose, acetate) to electrical energy through the biochemical
problems. In the last decade, microbial fuel cells (MFCs) have reactions of anaerobic bacteria in the anode chamber [2].

Abbreviation: 2L, two-layer cathode structure composed of catalyst layer and gas diffusion layer (CL þ GDL); 3L, three-layer cathode
structure composed of catalyst layer, micro porous layer and gas diffusion layer (CL þ MPL þ GDL); CBL, carbon based layer; CL, catalyst
layer; COD, Chemical oxygen demand; Ecell, Overall open circuit potential (OCPcathodeOCPanode); GAC, granulated activated carbon; GDL,
gas diffusion layer; ML, multi-layer cathode structure composed of catalyst layer, gas diffusion layer, carbon based layer and four PTFE
layers (CL þ GDL þ CBLþ4 PTFE layers); MPL, micro porous layer; OCP, Open circuit potential (anodic or cathodic); ORR, Oxygen reduction
reaction; PTFE, polytetrafluoroethylene; Rohmic, Ohmic resistance; SCMFC, Single-chamber microbial fuel cell.
* Corresponding author. Department of Civil and Environmental Engineering, University of Connecticut, Storrs, CT 06269, USA.
Tel.: þ1 860 486 2339; fax: þ1 860 486 2298.
E-mail address: baikun@engr.uconn.edu (B. Li).
0360-3199/$ e see front matter Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.07.030
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 3 0 9 6 e1 3 1 0 4 13097

Anaerobic bacteria degrade the organic compounds at the

anode and produce electrons and protons. The protons are
released into the anodic solution, whereas the electrons then
transfer through the external circuit to the cathode chamber
where they react with oxygen to form water.
Biofilm growth on anode surface is critical for electron
generation and organic substrate removal in MFCs. Many
studies have focused on anode materials [4e6], bacteria
species [7,8], organic substrates [9e11] and MFC operational
conditions [2e4,9e13]. In recent years, it has been found that
cathode properties are equally important for power genera-
tion in MFCs [14e19]. By using a polymeric membrane to
separate the anode and the cathode, the problems of cathode
flooding and biofilm growth on cathodes were mitigated
[18,19]. However, the use of polymer membranes is limited by
high cost and high ohmic resistance (Rohmic). Removing the
polymer membrane can lower the Rohmic and improve the
power generation of MFCs [3]. But two major problems of
cathodes, namely biofilm growth and cathode flooding, are
significant in membrane-less MFCs. Biofilms growing on the
water-facing side of cathodes consume oxygen at the cathode,
increase the Rohmic of MFCs, and lower the overall power
output [16,17]. Electrode flooding (the penetration of water
into the cathode structure) notably limits oxygen transport
through the cathode, and lowers power generation [20e23],
which is a well-known problem in conventional low temper-
ature fuel cells, but has not been thoroughly studied in MFCs.
Most cathodes used in conventional hydrogen fuel cells
have a two-layer (2L) or three-layer (3L) structure [20e22]. The
two-layer (2L) cathode structure is composed of a catalyst
layer (CL) and a gas diffusion layer (GDL) (Fig. 1a) [20e22],
while the three-layer (3L) cathode structure is composed of CL,
a GDL and a micro porous layer (MPL), with the MPL between
the CL and the GDL (Fig. 1b) [20e22]. The CL directly contacts
the water (or polymer membrane) in MFCs and is composed of
a mixture of platinum (Pt) supported on nano-sized carbon
particles (as electro-catalyst) and ionomer solution (e.g.,
Nafion) [17,26]. The CL accelerates the oxygen reduction
reaction occurring at the cathode by lowering the activation Fig. 1 e The diagrams of (a) two-layer (2L), (b) three-layer
energy. The GDL, which consists of a macro-porous carbon (3L), and (c) multiple-layer (ML) cathode configurations (the
fiber material (pore size: 10e30 mm) [20e22], is a thick layer thickness of the single layers is not to scale).
located between the air and the MPL. It serves as a mechanical
support for the CL and MPL [20], collects electrons generated in
the anode, and allows transfer of oxygen from the air to the composed of a carbon/PTFE base layer. The outer (air-facing)
cathode structure to sustain oxygen reduction reaction (ORR) side of the CBL is coated with four layers of hydrophobic
[20]. In addition, the GDL is coated with hydrophobic materials compounds (e.g. PTFE) to reduce water loss from MFCs to air.
(e.g. polytetrafluoroethylene (PTFE)) for removing water The cathode structures currently used in the membrane-less
produced in the CL to avoid cathode flooding [20e22]. The MPL MFCs have the problems of water flooding, biofouling, and
is a conductive ink applied on the GDL and has small pore low oxygen reduction reaction (ORR) rate. For example, most
sizes of 0.1e1 mm [20e22], which can prevent the condensa- of the 2L cathode structures lack the polymeric membrane
tion of the water produced on cathodes [22]. It has been found electrolyte, which results in significant water loss due to the
that the MPL reduces water transfer throughout the cathode large pore size of the GDL (Fig. 1a) [17].
structures, and effectively prevents cathode flooding in The overall objective of this study was to investigate a 3L
conventional fuel cells [20e22]. cathode structure that has been used in conventional
The commonly used cathode structures in MFCs have hydrogen fuel cells to mitigate the biofilm growth and cathode
multiple-layer (ML) structures consisting of CL, GDL, carbon flooding problems in MFCs. The 3L cathode structure was
based layer (CBL) and PTFE layers (Fig. 1c) [15e17]. The CL is developed by incorporating an MPL between the CL and GDL.
directly contacted with water in the anode chamber. The GDL There were three tasks in this study. First, water loss through
is on the top of the CL and composed of PTFE treated carbon different cathode structures (2L, 3L and ML) with different
cloth for high hydrophobicity. The CBL is next to the GDL and PTFE coatings (wt%) was measured to determine the optimal
13098 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 3 0 9 6 e1 3 1 0 4

cathode structures for the lowest water loss. Second, biofilm 2.2. MFC setup and operation
growth on cathode surfaces was investigated to elucidate the
penetration of biofilms into the cathode structures and The MFCs used in this study were single-chamber microbial
determine its effects on water loss and MFCs performance. fuel cells (SCMFCs) operated in batch-mode without mixing.
Third, the power generation and organic substrate removal in The configuration was described in previous works of our
MFCs with different cathode structures were compared to group [5,11,14]. Compared with traditional two-chamber
determine the best cathode structure under different organic MFCs, the proton exchange membrane (PEM) was removed
loadings. in the SCMFCs to simplify the configuration, reduce internal
resistance (Rin), and utilize atmospheric oxygen in air for
oxygen reduction on cathodes to accelerate cathodic reactions
and electron acceptance. The volume of the SCMFC was 0.13 L.
2. Materials and method
About 20 g of granular activated carbon (GAC, GC 8  30,
General Carbon, Paterson, NJ) was used as the supporting
2.1. Cathodes
medium for anaerobic anodophilic bacteria in the anode
chamber. Clean carbon cloth (non-wet proofed, E-Tek)
Sigracet S35 (SGL Carbon) carbon paper was used as GDL for
(geometric area: 4 cm2) was placed inside the GAC bed and
making five cathodes (2L and 3L). These cathodes were made
used as the anode. The cathodes to be examined (geometric
on the same GDL substrate with the same carbon paper
area: 6 cm2) were fixed on the lower part of the SCMFCs, with
density, pore size 10e30 mm [20e22,25], but different amounts
the CL side facing the water and the PTFE side of the GDL
of PTFE. The commercial names of each cathode consisted of
facing the air. The anode and cathode were connected using
carbon paper (Sigracet SGL S35), the types of PTFE treatment
an external circuit with an external resistance (Rext) of 100 U.
(A: untreated, B: 5%wt PTFE treated, and D: 20%wt PTFE
The voltage over Rext was recorded by a Keithley 2700 data
treated), and the addition of MPL (A: without MPL, and C: with
logging system at 2 h intervals.
MPL) (Table 1). The MPL is usually a mixture of carbon black
The influent collected at the University of Connecticut
(e.g. Vulcan XC-72), PTFE dispersion, surfactant and solvent
Wastewater Treatment Plant contained diverse anaerobic
(e.g. isopropanol) [20,21,25,26]. The MPL is usually formulated
anodophilic bacteria and was used as the inoculum in
as a slurry with the solid percentage less than 20%wt [26].
SCMFCs. The initial chemical oxygen demand (COD) of
Therefore, the MPL is applied to the GDL surface using spraying
wastewater was about 0.3 g/L. Three levels of COD concen-
techniques in a three-step procedure including heating to
trations (0.7, 1.5 and 3.0 g/L) were examined. All the experi-
allow solvent evaporation, surfactant volatilization, and PTFE
ments were conducted at a constant temperature of 30  C in
sintering [26]. The CL was based on Pt catalyst (0.5 mgPt/cm2
an incubator.
loading, Baltic Fuel Cells GMBH) on the water-facing side.
All these five cathodes structures (2L and 3L) were
2.3. Water loss measurements
compared with an ML cathode carbon cloth based (wet proo-
fed with 30%wt PTFE, E-Tek, FL) with a mixture of carbon black
Water loss was investigated for each cathode to determine the
(Vulcan XC-72) and PTFE solution being coated on the air side
capability of the GDL and MPL to hold water in SCMFCs. Before
of the GDL to create a carbon based layer (CBL), and finally four
the measurement, the anode chamber (volume: 0.13 L) was
additional layers of a PTFE solution (60%wt) were coated on
filled with wastewater and then sealed. The six cathodes (2L-0,
the top of the CBL side (as shown in Fig. 1c) [17]. For this ML
2L-5, 2L-20, 3L-5, 3L-20, and ML) (listed in Table 1) were indi-
cathode, the Pt catalyst applied was a loading of 0.5 mgPt/cm2
vidually tested in the SCMFCs in two trials. The SCMFCs were
on the water-facing side [17].
put into an incubator with the controlled humidity of 19% and
Briefly, three 2L cathode structures (2L-0 (GDL with no PTFE
the temperatures ranging from 25  C to 40  C. These temper-
coated), 2L-5 (GDL 5%wt PTFE treated), and 2L-20 (GDL 20%wt
atures are typically optimal temperatures for anaerobic mes-
PTFE treated)), two 3L cathode structures (3L-5 (GDL 5%wt
ophilic bacteria. The entire weight of each SCMFC system was
PTFE treated) and 3L-20 (GDL 20%wt PTFE treated)), and one
measured daily throughout the experimental period using
ML cathode (GDL 30%wt PTFE treated) were examined in this
a balance (PR503 Mettler Toledo, accuracy: 0.001 g) to deter-
study.
mine the water loss for each cathode at different tempera-
tures. The water loss was measured at the beginning and at
the end of the experimentation with the cathode in abiotic
Table 1 e The characteristics of the 2L, 3L and ML (clean cathode) and biotic (biofilm colonized cathode) condi-
cathodes tested in SCMFCs. tions, respectively.
Cathode PTFE content Presence of Layers Commercial
name in GDL [%wt] MPL/PTFE ML name 2.4. Chemical oxygen demand (COD) measurements in
2L-0 0 None 2L SGL-S35AA MFCs
2L-5 5 None 2L SGL-S35BA
2L-20 20 None 2L SGL-S35DA The COD concentration of the anode solution was measured
3L-5 5 MPL 3L SGL-S35BC using HACH high range COD vials (100e15000 mg/L) and DR
3L-20 20 MPL 3L SGL-S35DC
220 spectroscopy (HACH, Loverland, CO) following the stan-
ML 30 4 PTFE ML e
dard procedure recommended by HACH. For each measure-
LAYERS
ment, 0.2 mL of water solution was taken from the anode
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chamber of the SCMFCs, filtered through a Millipore filter
membrane (pore size: 0.45 mm) and then put into a COD vial
containing potassium dichromate and digested at 150  C for
2 h. The COD concentrations were measured on the 3rd, 5th
and 10th days after the initial operation of SCMFCs.
2.5. Polarization curve measurement
Polarization curve measurements were conducted to deter-
mine the power generation at different Rext (33Ue1000U) [5,14].
The voltage over each Rext was recorded using a multimeter
until the steady state was reached (which usually took
2e5 min). The current output (I ) was calculated according to
I ¼ V/Rext, where V is the measured voltage. The current
density and power density per unit area were calculated using
V/RextA and V2/RextA, respectively, where A is the geometric
cathode area (6 cm2). The maximum power density was
derived from the polarization curve. Three polarization curves
were performed at each COD concentration (0.7, 1.5, and 3 g/L)
and the average values were calculated.
2.6. Ohmic resistance (Rohmic) and open circuit potential
(OCP) of MFCs
The internal resistance describes the ability of an MFC to resist
the flow of charge and result in voltage losses in the MFC.
Three losses comprise the internal resistance: activation,
ohmic and mass transfer (kinetic) [16]. In this study, only
ohmic resistance (Rohmic), caused by the electrical resistivity of
the materials (e.g., electrodes and electrolyte), was consid-
ered. Rohmic was measured by electrochemical impedance
spectroscopy (EIS) using a potentiostat (Bio-Logic Research
Potentiostat, Model VMP3) [5,11,14]. The Open Circuit Potential
(OCP) values of SCMFCs were measured using a potentiostat
(Gamry Reference 600) with the counter pole and reference
pole being connected to the reference Ag/AgCl electrode. The
anode OCP indicates the electrical potential of the anode
(where the oxidation of organic substrates occurs), and the
cathode OCP indicates the electrical potential of the cathode
(where oxygen reduction occurs). The overall ORP values (Ecell)
of SCMFCs equaled the cathode OCP minus the anode OCP
(OCPcathodeOCPanode).
2.7. Scanning electron microscopy (SEM) observation of
the cathodes after MFC tests
The biofilm growth on cathodes was observed using an SEM
(Model: Joel6335F) as previously described [14]. After
SCMFCs were operated for 120 days, the cathodes were
taken from the SCMFCs and fixed for 12 h at 4  C in a solu-
tion containing 2.5 vol% paraformaldehyde, 1.5 vol%
glutaraldehyde and 0.1M cacodylate buffer (pH 7.4). The
cathodes were then washed three times with cacodylate
buffer solution and dehydrated in a series of ethanol/water
solutions (the volume ratios of ethanol to water: 25%, 50%,
70%, 85%, 95%, and 100%) for 15 min [7]. Finally, each
cathode was dried in an anaerobic environment at 35  C and
sputtered with gold at 2.2 kV, 10 mA for 2 min before SEM
observation.
13099
3. Results and discussion
3.1. Effects of GDL and MPL on water loss on clean
cathodes
The tests of water loss on cathodes showed that water diffu-
sion fluxes varied with cathode structures and temperatures.
The water diffusion on cathodes was driven by the difference
of water content (or humidity) between the water-faced side
of cathodes and the air-faced side of cathodes. Due to the low
hydrostatic force on the cathodes in the lab-scale SCMFCs
configuration, the liquid water transport was negligible
[21,24]. Water flux ranged from 0.37  0.02 to 1.57  0.07 g/day/
cm2, which was similar to the reported values for conven-
tional fuel cell (0.2e2.5 g/day/cm2) [23,24,30]. The two-layer
(2L) cathode had higher water flux than the three-layer (3L)
and multiple-layer (ML) structures (Fig. 2). Specifically, the
water flux of the 2L cathodes with a 5%wt PTFE GDL (2L-5) was
13e20% higher than the 3L cathodes with a 5%wt PTFE GDL
(3L-5), and the water flux of the 2L cathodes with a 20%wt PTFE
GDL (2L-5) was 14e23% higher than the 3L cathode with a 20%
PTFE GDL (3L-5). In addition, the water flux through the
cathode increased with temperature from 25 to 40  C (Fig. 2),
which could be explained by faster evaporation at higher
temperature [24,30].
For the 3L cathodes, the addition of the MPL between the
GDL and CL substantially reduced the water flux probably due
to a lower porosity and to the small pore size (0.1e1 mm) of the
MPL. Two types of 3L cathodes (3L-5 and 3L-20) with PTFE
treatment had low water fluxes, with values of 0.37  0.02 g/
day/cm2 at 25  C and 1.04  0.04 g/day/cm2 at 40  C. For the ML
cathodes, water fluxes (0.40  0.03 g/day/cm2 at 25  C and
1.15  0.04 g/day/cm2 at 40  C) were lower than the 2L cath-
odes structures but slightly higher than the 3L cathode
structures (difference statistically not significant) (Fig. 2). The
four PTFE layers coated on the air-facing side of the ML
cathode enhanced the cathode hydrophobicity and reduced
the pore size of the cathode structure. Water loss tests have
verified that 3L and ML cathodes increase the water transport
resistance and lowering water flux [24,30].
3.2. The correlation of biofilm formation and water loss
on the cathodes
Biofilms growing on the water-facing side and the air-facing
side of cathodes were observed using a SEM after 120 days of
Fig. 2 e The water loss flux through the clean cathodes (2L,
3L and ML) at different temperatures (max stdv ± 6).
13100 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 3 0 9 6 e1 3 1 0 4
operation. All the cathodes had biofilms formed on the water-
facing side, while the biofilm formation on the air-facing side
varied with cathode structures. The biofilms formed on the
air-facing side of all the 2L cathodes, regardless of PTFE
treatment (2L-0, 2L-5 and 2L-20) (Fig. 3a, 3b and 3c). These
results indicated that the large pore sizes (10e30 mm) of the
GDL on these 2L cathodes might not be able to stop bacterial
penetration through the GDL and led to the penetration of
biofilms from the CL side to the air side.
In the case of the 3L cathodes (3L-5 and 3L-20), the addition
of MPL between GDL and CL could prevent the penetration of
biofilms through the GDL. The biofilm formation was only
detected on the water-facing side of the cathodes, while there
was no biofilm formed on the air-facing side (Fig. 3d and 3e).
This might be explained by the small pore sizes (0.1e1 mm) of
MPL that could stop the penetration of bacterial cells from the
water side to the air side. In the ML cathodes, the addition of
Fig. 3 e The SEM pictures of the air side of the different cathode structures after 120 days of MFC operation (a.2L-0 b. 2L-5 c.
2L-20 d. 3L-5 e. 3L-20 f. ML).
four PTFE layers on the air-facing side of the GDL produced
a compact and hydrophobic layer similar to the MPL on the 3L
cathodes. As demonstrated in the water flux tests, the water
flux of the ML cathodes was lower than that of the 2L cathodes
(Fig. 2). Thus, the biofilms formed on the water-facing side of
the ML cathodes might partially penetrate into the GDL layer,
but they were stopped at the four layers of PTFE, so that there
was no biofilm formation on the air-facing side (Fig. 3f).
There was a close correlation between the biofilm growth
and water flux of the cathodes. Water flux had been found to
decrease with thicker biofilms on the water-facing side of the
cathodes [16], which was probably caused by the high mass
transport resistance after biofilm growth. However, some of
our results were in contrast with these findings. Biofilm
penetration was detected on the 2L cathodes (Fig. 3aec),
which also had higher water flux (Fig. 3). This suggests that the
biofilm penetration might create a pathway for water to pass
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 3 0 9 6 e1 3 1 0 4
Table 2 e The water loss flux [g/day/cm2] through different cathode structures in SCMFCs at 30  C.
2L-0
Clean cathode 0.75
Cathodes after 120 days of operation 6.99
through the cathode structure. The water flux of the 2L cath-
odes with biofilm formation was 6.5e70.1 g/day/cm2 after
120 days of operation (at 30  C, Table 2), which was 10 times
higher than that of the clean 2L cathodes (Fig. 2). The 3L and
ML cathodes solved the problems of biofilm penetration, and
the water flux was substantially reduced to 0.47e0.52  0.03 g/
day/cm2, which was similar to the clean cathodes (Table 2).
Due to the smaller pore size of the MPL on the 3L cathodes and
the PTFE layers on the ML cathodes, the biofilms formed on
the water-facing side could not penetrate throughout the
cathode structures, and served as an additional layer on the
cathodes to increase the water transport resistance.
3.3. Effects of GDL and MPL on ohmic resistance (Rohmic)
and OCP of MFCs
Electrochemical properties (e.g. Rohmic and OCP) were
measured in SCMFCs with different cathode structures. Rohmic
has two components: the electrolyte ohmic loss caused by the
solution resistance and the electrode ohmic loss caused by the
transport of electrons through electrodes [14]. Because the
SCMFCs used in this study were identical in configuration,
volume, dimension, anode material, anode solution, electrode
distance, and organic substrate types, the differences of Rohmic
among these SCMFCs could be attributed to the cathode
structures. The results showed that the presence of an MPL in
cathode structures reduced Rohmic of SCMFCs. The 3L cathodes
(3L-5 and 3L-20) had lower Rohmic (26e34 U) than the PTFE
treated 2L cathodes (2L-5 and 2L-20) (88e94 U) and the ML
cathodes (69 U), and the untreated 2L cathode (2L-0) had the
highest Rohmic (105 U) (Table 3). The mean reason for the low
Rohmic in the 3L cathodes is probably due to the fine carbon
particles of the MPL that penetrate into the carbon matrix of
the GDL, enhance the contact between GDL and CL, and thus
increasing the overall cathode conductivity. This advantage of
3L cathode to lower Rohmic had been found in previous studies
of conventional fuel cells [27e29].
On the other hand, biofilm growth on the cathodes severely
reduced the electrical conductivities and increased Rohmic (as
indicated by the higher Rohmic of 2L cathodes). The 2L cathodes
had the lowest electrical conductivity probably due to the
higher extent of biofilm growth, the penetration of biofilms
throughout the cathodes (Fig. 3aec), and poorer contact
Table 3 e The ohmic resistance (Rohmic) and open circuit potential (OCP) of the SCMFCs with different carbon structures.
2L-0 2L-5
Rohmic (U) 105 88
Anodic OCP (mV vs Ag/AgCl) 450 468
Cathode OCP (mV vs Ag/AgCl) 111 134
Ecell (mV) 561 602
13101
2L-5 2L-20 3L-5 3L-20 ML
0.63 0.62 0.55 0.54 0.57
6.66 6.51 0.48 0.47 0.52
between GDL and CL [27,28]. The 3L cathodes had a high
electrical conductivity and prevented biofilms from growing
through the cathode structures (Fig. 3d and e). The Rohmic of
the ML cathodes was lower than that of the 2L cathodes, but
higher than that of 3L cathodes, which might be due to the
four hydrophobic PTFE layers coated on the outer side of the
GDL that partially prevent the biofilm growth (Fig. 3f). It should
be noted that the higher PTFE contents on the GDL (from 5% wt
PTFE to 20%wt PTFE) in the 2L and 3L cathodes slightly
increased Rohmic by 6e8 U (Table 3), probably due to the higher
electrons transfer resistance [27e29]. The values of Rohmic
obtained in this study for 3L cathodes were similar to prior
literature results (20e24 U) [31], as were the Rohmic values of 2L
and ML cathodes (40e100 U) [5,32,33].
Because all SCMFCs tested had the same anode materials
and the same anode chamber, the anodic OCP values were
similar (450 to 468 mV vs Ag/AgCl) (Table 3). In contrast, the
cathodic OCP values varied from 111 mV vs Ag/AgCl (2L
cathodes) to 191 mV vs Ag/AgCl (3L cathodes), which led to
different overall Ecell values of SCMFCs (561e602 mV with 2L
cathodes, 590 mV with ML cathodes, and 641e655 mV with 3L
cathodes). The higher OCPcathode values had been found to
correlate with higher oxygen reaction rates (ORR) [34]. Thus,
these OCPcathode results implied that the ORR on the 3L cath-
odes might be faster than that on the 2L and ML cathodes.
3.4. Effects of GDL and MPL on power generation of
MFCs
The power density of SCMFCs with different cathode struc-
tures was examined at three COD concentrations (0.7, 1.5 and
3 g/L), and correlated with the electrochemical characteristics
(Rohmic, Ecell and OCPcathode). Due to their lower Rohmic and
higher OCP values (Table 3), the SCMFCs with the 3L cathodes
were expected to have a better cathodic reaction and greater
power generation than those with the 2L cathodes and the ML
cathodes. The increase in power generation with COD
concentration had been found in other studies [5,16], which
was caused by higher solution conductivity and more
substrates available to the anode-supported bacteria. The
results of this study followed the same trend. The power
density of all SCMFCs tested reached the highest power
generation at the COD concentration of 3 g/L (Fig. 4a). The
2L-20 3L-5 3L-20 ML
94 26 34 69
462 464 458 465
136 191 183 125
598 655 641 590
13102 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 3 0 9 6 e1 3 1 0 4

cathodes (Fig. 3f), but still could not effectively solve the
oxygen transfer resistance problem. It had been found that
the water formed in the oxygen reduction reactions (ORR)
condensed on the GDL of cathodes in conventional fuel cells,
the removal of water was hindered by the hydrophobic PTFE
layers, and finally led to cathode flooding [3,20e23].
The maximum power generation of MFCs depends on
several factors including the presence of a polymeric
membrane, electrode materials, electrode dimensions, the
distance between electrodes [5,35], anode/cathode chamber
configurations, MFC volume, COD concentrations [34],
substrate types [11] and microbial populations [36,37]. Because
the main goal of this study was to investigate the effects of
different cathode structures (2L, 3L and ML) on power gener-
ation and COD removal in MFC systems, the optimization of
MFC configuration for higher power generation was not the
focus of this study. Therefore, the maximum power genera-
tion obtained with a 3L cathode structure (501 mW/m2) in this
study was lower than the previously reported result (766 mW/
m2) with an ML cathode structure [17]. It had been reported
that shorter electrode distance [5,35] and the use of selected
pure microorganisms and the precolonized anodes [2,36e38]
enhanced power generation. Compared with the previous
study [17], our system (1) had a longer electrode distance (7 cm
vs 4 cm), which would substantially increase Rohmic and lower
the power generation; (2) used raw wastewater and sodium
acetate instead of pure nutrients and synthetic wastewater,
which would lower the power generation; and (3) had
a smaller geometric anode area (4 cm2 vs 7 cm2), which can
significantly reduce the power generation.

3.5. Effects of GDL and MPL on COD removal in MFCs

Power generation and organic substrate removal were closely

correlated, since organic substrates in wastewater are the
fuels for anaerobic bacteria in MFCs. Organic substrate
removal was studied at three levels of COD concentrations
(0.7, 1.5 and 3 g/L) in SCMFCs. COD concentration steadily
Fig. 4 e The power generation of SCMFCs at different COD
dropped during the operational period (3e10 days) (Fig. 5). The
concentrations (a: 3 gCOD/L (max stdv ± 6%), b: 1.5 g/L (max
COD removal efficiency was well correlated with power
stdv ± 5%), and c: 0.7 mg/L (max stdv ± 3%)).
generation (Fig. 4), indicating that high reaction rates in the
SCMFCs with 3L cathodes led to high power generation and
efficient substrate removal.
power generation decreased by 17e20% in all the SCMFCs at Previous studies of continuous-mode MFCs found that the
the COD concentration of 1.5 g/L (Fig. 4b). The power genera- power generation was a function of substrate removal rate in
tion further decreased 16e22% at the COD concentration of the COD loadings of 0.21e4.44 kg/m3/day [39] and in COD
0.7 g/L (Fig. 4c).
The power generation results confirmed that the presence
of the MPL on the 3L cathodes (3L-5 and 3L-20) significantly
increased the MFC performance in all COD concentrations
tested (Fig. 4). Due to the small pore size of the MPL, biofilm
growth was prevented inside the 3L cathodes (Fig. 3d and e),
which was expected to provide a free pathway for oxygen to
reach the CL layer of cathodes and facilitate the cathodic
reactions. In contrast, the 2L cathodes had biofilm formation
on both sides of the cathodes (Fig. 3aec), which might
consume oxygen, increase the oxygen transport resistance to
reach the CL layer, and lower the electron acceptance capa-
bility of the cathodes. The ML cathodes with four layers of Fig. 5 e COD degradation in SCMFCs with different cathode
PTFE prevented the biofilm penetration compared with the 2L structures.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 3 0 9 6 e1 3 1 0 4
concentrations of 100e600 mg/L [40]. Our batch-mode MFC
tests found that the substrate removal rate increased from
130e186 to 144e235 mgCOD/L/day over the COD concentra-
tions of 0.7 g/L and 1.5 g/L, but stabilized at 140e228 mgCOD/L/
day at the COD concentration of 3 g/L, while the power
generation of all SCMFCs tested steadily increased with COD
concentration and reached the peak values at 3 g/L COD
(Fig. 4). This is probably because the small anode area (4 cm2)
utilized in this study caused the anode processes (e.g. biofilm
growth and electron collection) to become the limiting factors.
When COD concentrations increased from 0.7 to 1.5 g/L in the
anodic solution, anaerobic bacteria had more organic
substrate to grow and generate more electricity. At the COD
concentration of 3 g/L, the bacterial activity and the substrate
degradation rate probably remained the same as at 1.5 g/L
COD due to the small anode area, but since the high COD
concentrations increased the solution conductivity and
reduced Rohmic, the power generation still increased at the
COD of 3 g/L [5].
For MFC application in wastewater treatment plants, the
leakage of water (or pollutants) outside the MFC cathodes
should be avoided. The results showed that 2L cathode
structures had the highest water loss (Fig. 2) and cannot be
a candidate for large scale applications. Based on the results of
power generation and COD removal, the 3L cathode structures
offered a promising alternative to inhibit biofilm penetration
throughout the cathodes and prevent cathode flooding,
thereby facilitating oxygen transfer through the cathodes and
accelerating the ORR. Due the small pore size of the MPL and
the lower contact resistance between GDL and CL, the 3L
cathode structure showed the highest electrical conductivity
among the cathodes tested in this study. Additionally, the
prevention of biofilm penetration could prolong the durability
of the cathodes. In terms of the cathode costs, the 3L cathodes
are much cheaper than the commonly used ML cathodes in
MFC systems, since the 3L cathodes use much less PTFE. Based
on this batch-mode lab-scale SCMFC tests, the 3L cathode
structure with CL, MPL, and GDL is a promising electrode for
efficient, stable and robust MFC operation.
4. Conclusion
Three types of cathode structures (2L, 3L and ML) were
compared in SCMFCs in this study. The effects of adding an
MPL between the CL and GDL on water loss, biofilm growth,
power generation, and COD removal were extensively exam-
ined. Three major conclusions were drawn.
First, the 3L cathodes (with MPL) exhibited lower water loss
and lower extents of biofilm growth than the ML cathodes or
the 2L cathodes (no MPL). A clear correlation of biofilm pene-
tration into cathode structures and water loss was
established.
Second, the MFCs with the 3L cathodes had the lower
Rohmic(26e34 U), higher cathodic OCP (183e191 mV), and
higher power generation (501 mW/m2) than those with 2L
cathodes and mL cathodes. The MPL layer avoided cathode
flooding problems, prevented biofilm penetration through the
cathode structures, and thus improved power generation of
MFCs.
13103
Third, the MFCs with the 3L cathodes had higher COD
removal efficiencies (71e78%) than those with 2L cathodes
and ML cathodes. The 3L cathode structures with the MPL
inserted between the CL and GDL exhibited a great potential
for low water loss, high power generation, and efficient
contaminant removal.
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