Bioelectrochemistry 92 (2013) 2226

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Bioelectrochemistry
journal homepage: www.elsevier.com/locate/bioelechem

Short communication

Air-cathode preparation with activated carbon as catalyst, PTFE as

binder and nickel foam as current collector for microbial fuel cells
Shaoan Cheng , Jiancheng Wu
State Key Laboratory of Clean Energy, Department of Energy Engineering, Zhejiang University, Hangzhou 310027, PR China

a r t i c l e

i n f o

Article history:
Received 8 December 2012
Received in revised form 5 March 2013
Accepted 6 March 2013
Available online 13 March 2013
Keywords:
Microbial fuel cell
Nickel foam
Activated carbon
Air cathode
Bioenergy

a b s t r a c t
A cathode is a critical factor that limits the practical application of microbial fuel cells (MFCs) in terms of cost
and power generation. To develop a cost-effective cathode, we investigate a cathode preparation technique
using nickel foam as a current collector, activated carbon as a catalyst and PTFE as a binder. The effects of
the type and loading of conductive carbon, the type and loading of activated carbon, and PTFE loading on
cathode performance are systematically studied by linear sweep voltammetry (LSV). The nickel foam cathode
MFC produces a power density of 1190 50 mW m 2, comparable with 1320 mW m 2 from a typical
carbon cloth Pt cathode MFC. However, the cost of a nickel foam activated carbon cathode is 1/30 of that of
carbon cloth Pt cathode. The results indicate that a nickel foam cathode could be used in scaling up the
MFC system.
2013 Elsevier B.V. All rights reserved.

1. Introduction
As a potential technology for renewable energy production, microbial
fuel cells (MFC) have received great attention in recent years [13]. MFCs
could produce a certain amount of electricity while treating wastewater.
It could be considered a major technology for energy recovery from
wastewater in the future.
High cost and low power output are two major hurdles of MFC
development on a large scale. The cathode accounts for the main part
of these problems due to the high cost of its components and slow
kinetics of oxygen reduction at neutral medium. In order to overcome
these bottlenecks researchers have investigated alternative catalysts
to Pt [4,5], different oxidants as electron acceptors [68], different pHs
[9], different binders [10] and the structure of the diffusion layer [6].
cobalt tetramethoxyphenyl porphyrin (CoTMPP), iron phthalocyanin
(FePC) and manganese dioxide (MnO2) can serve as alternative catalysts to Pt [1013]. Inexpensive PTFE solutions can be used in place of
a Naon solution as a catalyst binder. Recently, a non-metal cathode
made with activated carbon and PTFE showed a comparable performance with a Pt cathode, but with a much lower cost [14]. There are
also a few works presented on using a hydrophilic ionomer and an
anion exchange ionomer as the binder for an oxygen reduction catalyst
in an MFC, showing an improved activity for catalysts than using PTFE
[15,16]. The cathode contributes a high percentage of internal resistance of MFC [17]. In addition to the catalyst and binder, the cathode
current collector also plays an important role in cathode performance
and cost. The most common current collector material is carbon cloth,
Corresponding author. Tel.: +86 571 87952038; fax: +86 571 87951616.
E-mail address: shaoancheng@zju.edu.cn (S. Cheng).
1567-5394/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.bioelechem.2013.03.001

which is expensive ($1000 m2). A stainless steel mesh or a nickel

mesh have been studied as current collector in MFC, showing high
power density and low cost [14,18]. However, in these studies, the current collector had a two-dimensional structure, on which the catalyst
layer was coated or pressed. The formed cathode structure could cause
increased ohmic resistance, especially for a cathode made of PTFE and
activated carbon (AC), because they have no or low conductivity [14].
Thus, the cathode performance is still the limiting factor of MFC development [17,19].
Nickel foam has a three-dimensional structure with high porosity
and high conductivity. The porous framework of nickel foam is lled
with catalyst paste such as the mixture of activated carbon and PTFE
binder, resulting in a decrease in ohmic resistance and an increase in
catalyst utilization. Nickel foam has a good corrosion resistance in alkaline and neutral medium, but corrodes in acid media. Nickel foam is
widely used as a current collector in alkaline batteries [20]. Recently,
Liu et al. reported an air-cathode made of nickel foam, Pt catalyst and
Naon binder [21]. In their study, Naon solution was used as a catalyst
binder, which exposed the nickel foam to an acidic environment and
caused it to corrode. In order to prevent corrosion of nickel foam in
the acid environment (Naon solution as the catalyst binder), the nickel
foam was coated with PTFE (30 wt.% solution) [21]. However, the PTFE
coated on the surface of the nickel foam increased the electric resistance
between the metal matrix current collector and the catalyst layer due to
the electrically non-conductive property of PTFE. The power density
with PTFE-coated nickel foam cathode was not improved compared
with the carbon cloth cathode [21].
In this study, we report a new air-cathode made of nickel foam as
a current collector, activated carbon as catalyst and PTFE as a diffusion
layer and catalyst binder. The preparation technology was optimized

S. Cheng, J. Wu / Bioelectrochemistry 92 (2013) 2226

through the study of catalyst type and loading, conductive addition material and PTFE loading. The performance of nickel foam air-cathode
was evaluated using linear sweep voltammetry (LSV).
2. Materials and methods
2.1. Preparation of cathode
The nickel foam cathodes were composed of the nickel foam
current collector, the conductive carbon base diffusion layer, the
PTFE diffusion layer and the catalyst layer. Nickel foam was used as
supplied (Changle New Technology Electronics Co., Ltd, China). The
conductive carbon diffusion layers were made by applying a mixture
of carbon powder (6 mg cm 2) and PTFE (15 mg cm 2) onto one
side of the nickel foam. The PTFE diffusion layer was formed by coating 60% the PTFE solution (Yilida Power Source Co., Ltd, China) on the
surface of the carbon base layer, which was subsequently heated for
30 min at 370 C as previously described [22]. The conductive carbon
diffusion layer and the PTFE diffusion layer together play a part in
preventing water leakage, salting-out and controlling oxygen diffusion.
Unless otherwise stated, the carbon base diffusion layer was made of a
mixture of F900-CC (Tianjin Yiborui Carbon Co. Ltd, China) 6 mg cm2,
PTFE 15 mg cm2 and Isopropyl alcohol 84 L cm2, and four PTFE
diffusion layers were applied onto one side of the nickel foam as previously described [23]. The catalyst layer was prepared by pasting a mixture of activated carbon, conductive carbon, PTFE and isopropyl alcohol
onto the other side of the nickel foam, which was subsequently heated
at 370 C for 30 min. Unless otherwise stated, the catalyst layer was
prepared with activated carbon 20 mg cm2, and conductive carbon,
PTFE, isopropyl alcohol (per cm2 of nickel foam) 0.8 mg, 6 mg, 40 L,
respectively. Finally, the formed cathode was rolled to a thickness of
1 mm using a roller (DYG-703, Dali Electric Co., Ltd, China).
Two kinds of activated carbon (having a high porous structure, but
a low conductivity), supercapacitor activated carbon (S-AC, Shanghai
Heda Carbon Materials Co., Ltd, China) and Nano activated carbon
(Nano-AC, Shanghai Hainuo Carbon Co., Ltd, China), were used as catalysts in the study. S-AC was used to investigate the effect of catalyst
loading on the performance of cathode, and its loadings were varied at 10,
15 and 20 mg cm2. Conductive carbon (having a high conductivity,
but a low porous structure) was mixed with a catalyst to improve the
conductivity of the catalyst layer. The conductive carbons tested are
Nano conductive carbon (Nano-CC, Shanghai Hainuo Carbon Co., Ltd,
China), 3000 mesh conductive carbon (3000-CC, Shanghai Hainuo Carbon Co., Ltd, China), XC-72 (XC-72, Wuxi Sophie Roland International
Trading Co. Ltd, China), and F900 carbon (F900-CC).
For the comparison study, air-cathodes using carbon cloth (30%
wet-proofed, E-TEK) or stainless steel (#30 mesh, 0.30 mm wire
diameter) as current collector were prepared with the same preparation
method as described above.
2.2. MFC setup and operation
Single-chambered air cathode cubic-shaped MFCs (26 mL liquid
volume, 4 cm anode chamber) were constructed as previously reported
[24] and were used to investigate the power density at various cathodes
using carbon ber brush anodes (25 mm diameter, 25 mm length).
The anodes were taken from the MFC reactors that were inoculated
with the primary clarier overow of the local wastewater treatment plant and operated using acetate (1.0 g L 1) as fuel for over
half a year. The MFCs were operated using 1.0 g L 1 sodium acetate
as fuel in 50 mM phosphate buffer solution (PBS, pH 7.0) containing
(per liter deionized water): KCl, 0.13 g L 1; NaH2PO4 2H2O,
2.75 g L 1; Na2HPO4 12H2O, 11.466 g L 1; NH4Cl, 0.31 g L 1,
and metal (12.5 mL L 1) and vitamins (5 mL L 1) [25]. The chamber
was relled when the voltage decreased to less than 50 mV. The polarization curves and the power densities are measured after MFCs were

23

operated with 1000 resistor for 40 relled times (around 60 days).

Each MFC test was conducted in triplicate.
2.3. Analysis
Cathode performance was evaluated with LSV conducted by a
potentiostat (CHI660D, Shanghai Chenhua Instrument Co. Ltd) in a
three-electrode-setup electrochemical cell. The electrochemical cell
was built as a 2 cm-cubic single-chamber reactor [15]. A Pt plate
(6 cm2 projected surface area) was used as counter electrode (anode).
The studied cathode (7 cm2 projected surface area) was used as working electrode (set up in the same way as that in a MFC). An Ag/AgCl electrode (0.201 vs SHE) was used as reference electrode located close to
the working electrode. All potentials refer to the Ag/AgCl reference electrode in the paper. LSV was typically conducted in 50 mM PBS with a
potential range from 0.2 to 0.2 V at the scan rate of 1 mV s1. Because the working potential of an air cathode in the MFC was mostly
in the region from 0.05 to 0.2 V, the currents that responded in this
cathode potential region in LSV were typically used to evaluate the cathode performance in this paper. Every designed cathode was tested in
triplicate. Each LSV test of cathode was conducted in three scans. The
data of current, potential and power density are reported in average.
All experiments were conducted in a 30 C temperature controlled
room.
Voltage (V) across an external resistance (1000 , unless otherwise
noted) was measured using a multimeter with a data acquisition system (2700, Keithley, U.S.) and used to calculate the power (P) according
to P = I V. Power density was then calculated using the power normalized by the projected surface area of the cathode. A polarization curve
was measured by varying the external resistance from 1000 to 50 .
3. Results and discussion
3.1. The effect of preparation conditions on the performance of nickel
foam cathode
The current of a cathode with Nano-AC (Nano activated carbon) is
signicantly lower than that of a cathode with S-AC (supercapacitor
activated carbon) in the potential region from 0.0 to 0.2 V (Fig. 1-A).
The Nano-AC cathode has 7.7 0.2 mA at 0.2 V, while the S-AC
has 8.9 0.5 mA, which is 13% higher. Nano-AC has a particle size of
200 nm and a specic surface area of 1350 m2 g 1, while S-AC has a
particle size of 5 m and a specic surface area of 2000 100 m2 g 1.
These results indicate that the high surface area of activated carbon is
the critical factor in cathode performance, not the particle size.
Increasing catalyst loading has a signicant effect on the cathode
performance in the studied potential region (Fig. 1-B). For example,
the reduction current increases from 0.4 0.2 to 1.1 0.2 mA
at 0.1 V, and from 6.6 0.2 to 7.3 0.3 mA at 0.2 V when
the catalyst loading increases from 10 to 15 mg cm 2. Further increasing catalyst loading from 15 to 20 increases reduction current
in the low potential region below 0.05 V, but has no signicant effect
on reduction current in the high potential region over 0.05 V. The
highest reduction current with the catalyst loading of 20 mg cm 2
at 0.2 V is 8.0 0.4 mA, which is 24% higher than a cathode
with a catalyst load of 10 mg cm 2. These results indicate that a
high catalyst loading has more contribution to performance improvement in the low potential region (high reduction current).
3000-CC (3000 mesh conductive carbon) and F900-CC (F900 carbon)
show a slightly better performance, with a current of 8.0 0.2 mA
and 7.8 0.1 mA at 0.2 V, respectively (Fig. 1-C). Nano-CC
(Nano conductive carbon) shows a lower performance with current of
7.5 0.2 mA, while XC-72 (XC-72 carbon) shows the lowest current
of 6.8 0.1 mA. F900-CC should be the best choice of conductive
carbon because it costs far less than the others.

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S. Cheng, J. Wu / Bioelectrochemistry 92 (2013) 2226

by the decrease in ohmic resistance of the catalyst layer as the PTFE

loading decreases. However, PTFE loading cannot be further decreased
below 0.3 mg PTFE per mg S-AC, at which point the catalyst powder
drops off the cathode surface after it dries.

2
0

I/mA

-2
3.2. A comparison of nickel foam cathode with carbon cloth cathode and
stainless steel cathode

-4
-6
Nano-AC

-10
-0.3

S-AC

-0.2

-0.1

0.1

0.2

E/V (vs. Ag/AgCl)

B
2

I/mA

0
-2
-4

-8
-10
-0.3

10
15
20

-6

-0.2

-0.1

0.1

LSV (linear sweep voltammetry) studies show that a nickel foam

activated carbon cathode has a signicantly higher current than a
carbon cloth activated carbon cathode and a stainless steel activated
carbon cathode (Fig. 2A). The current of nickel foam cathode at
0.2 V is 8.4 0.4 mA, which is 11% higher than that of carbon
cloth cathode ( 7.5 0.2 mA) and 28% higher than that of stainless steel cathode (6.59 0.2 mA). In the MFC studies, the nickel
foam cathode MFC (NF) produces a maximum power density of
1190 50 mW m2, while a MFC with a carbon cloth cathode (CC)
has a 22% lower power density with 928 37 mW m2 (Fig. 2B).

2
0
0.2

E/V (vs. Ag/AgCl)

I/mA

-8

C
2

I/mA

-4

SS

-6

CC

-8

NF

-10
-0.3

-0.2

-0.1

0.1

0.2

E/V (vs. Ag/AgCl)

-2
-4

XC-72
Nano-CC
3000-CC
F900-CC

-6
-8
-10
-0.3

-2

-0.2

-0.1

0.1

0.2

E/V (vs. Ag/AgCl)

2
0

I/mA

-2
-4
-6
-8
-10
-0.3

0.7
0.5
0.3
-0.2

-0.1

0.1

0.2

E/V (vs. Ag/AgCl)

Fig. 1. The LSV of cathodes with: (A) Nano activated carbon (Nano-AC) and super capacitor activated carbon (S-AC); (B) different loading of activated carbon catalyst, numbers
stand for the loading of 10 mg cm2, 15 mg cm2 and 20 mg cm2, respectively;
(C) different conductive carbons in the catalyst layer: 3000 mesh conductive carbon;
nano conductive carbon; XC-72; F900 carbon; (D) different PTFE loadings, the numbers
show the PTFE loading of 0.3, 0.5 and 0.7 mg PTFE per mg-AC.

Decreasing PTFE (polytetrauoroethylene) in the catalyst layer

results in an increase in reduction current at 0.2 V (Fig. 1-D). The current is 7.8 0.2 mA at the PTFE loading of 0.7 mg PTFE per mg-AC.
When the PTFE loading decreases to 0.3 mg PTFE per mg S-AC, the
current increases by 12% to 8.8 0.3 mA. This increase is caused

Fig. 2. A comparison of the nickel foam cathode, carbon cloth cathode and stainless
steel cathode. (A) LSV. (B) Power density. (C) Electrode polarization. NF: nickel foam
cathode; CC: carbon cloth cathode; SS: stainless steel cathode; Ea: anode potential;
Ec: cathode potential.

S. Cheng, J. Wu / Bioelectrochemistry 92 (2013) 2226

The MFC with a stainless steel cathode (SS) has the lowest power density with 814 38 mW m 2. The polarization curves show that all the
anode potentials are similar for all three MFCs, but the cathode performances are much different with an increasing order: the nickel foam
cathode > carbon cloth cathode > stainless steel cathode (Fig. 2C),
which is consistent with the results of the LSV studies. The thicknesses
of nickel foam, carbon cloth and stainless steel are 1, 0.6 and 0.3 mm,
respectively. Nickel foam has a three-dimensional and porous structure
which allows the catalyst to ll and distribute into its porous frame,
resulting in a low ohmic resistance and high performance of the
cathode. The internal resistance of the nickel foam cathode measured
from polarization curves is 85 , which is 22% lower than that of the
carbon cloth cathode (109 ) and 26% lower than that of the stainless
steel cathode (115 ). Although the high conductivity of nickel foam
may partially contribute to increasing the cathode performance, the result that the carbon cloth with low conductivity performs better than
the stainless steel with high conductivity indicates that the structure
(the thickness of porous material) of the current collector is more important for increasing the cathode performance, and thus the power
density of the MFC.
The power density achieved here with nickel foam is comparable
with that produced with the Pt-carbon cloth cathode under the
same condition (1320 mW m 2) [26]. However, the cost of a nickel
foam activated carbon cathode is only $50 m 2, which is 1/30 of
that of a Pt carbon cloth cathode ($1500 m 2). These results are comparable to that reported with the cathode made with activated carbon
as a catalyst, PTFE as a binder and nickel mesh as a current collector
[14]. The nickel mesh has a two-dimensional structure which could
result in a high ohmic resistance of cathode when the electrode was
scaled up, while the nickel foam activated carbon cathode could keep
a low resistance.
The performance of the nickel foam activated carbon cathode is
inuenced by the type and amount of activated carbon, the type of
conductive carbon, and PTFE loading. The best performance is achieved
with the cathode that contained (1) the catalyst layer prepared with
20 mg cm2 S-AC, 6 mg cm2 PTFE, 0.8 mg cm2 F900-CC and
40 L cm2 isopropyl alcohol; (2) the carbon base diffusion layer prepared with F900-CC 6 mg cm2, PTFE 15 mg cm2 and isopropyl alcohol 84 L cm2; (3) the diffusion layer prepared with 4 PTFE coatings.
The most important factors for improving cathode performance are
the structure of the current collector and the surface characteristic of
the catalyst. The activated carbons used here are commercial products
that are mostly used as the active materials in battery and capacitor.
Their surface characteristics well match the requirement of a battery
or a capacitor, but may not well match the requirement of the MFC
cathode to the oxygen reduction reaction. The surface characteristics
of activated carbon could be changed by treating activated carbon at a
high temperature [27] or in acid solution [28]. A further increase in performance of the nickel foam activated carbon cathode could be achieved
by modifying the surface characteristics of activated carbon with special
treatment technology.
The nickel foam corrodes in acid environments, but has good
corrosion resistance in neutral and alkaline media. Liu et al. [21]
have reported that a nickel foam cathode is seriously corroded during
the operation of a MFC when a bare nickel foam is used as a cathode
current collector with a Naon solution as a catalyst binder. However,
the corrosion of nickel foam is signicantly decreased by coating PTFE
on the surface of the nickel foam. The corrosion is likely due to the use
of Naon as a catalyst binder resulting in nickel foam being in an acid
environment. We do not measure corrosion of our PTFE bonded nickel foam cathode during the operation of MFC, but it is likely to be very
minor, based on the very stable performance of the MFC during
6 months of operation. Increasing PTFE loading in the catalyst layer
can prevent the corrosion of nickel foam, but increasing PTFE loading
resulted in a decrease in cathode performance (Fig. 1-D). However,
we recently found that the performance of a cathode with a high PTFE

25

loading in the catalyst layer can be signicantly improved by treating

the cathode with a solution, such as isopropyl alcohol. Details about
this treatment technology for treating cathode with chemicals will be
reported in the near future.
4. Conclusion
In this paper, a nickel foam cathode is prepared with nickel foam
as a current collector, activated carbon as a catalyst and PTFE as a
binder. The optimal conditions for the preparation of a nickel foam
cathode are: the catalyst layer prepared with 20 mg cm 2 S-AC,
6 mg cm 2 PTFE, 0.8 mg cm 2 F900-CC and 40 L cm 2 isopropyl
alcohol; the carbon base diffusion layer prepared with F900-CC
6 mg cm2, PTFE 15 mg cm2 and isopropyl alcohol 84 L cm2; and
the PTFE diffusion layer prepared with 4 PTFE coatings. Compared to
the carbon cloth cathode and stainless steel cathode, the nickel foam
cathode shows a higher performance and lower cost. Power production
is 1190 50 mW m2 with nickel foam activated carbon cathode,
comparable to 1320 mW m2 with typical carbon cloth Pt cathode.
However, the cost of nickel foam activated carbon cathode is 1/30 of
that of carbon cloth Pt cathode. These results show that the nickel foam
cathode is feasible for the MFC scale-up.
Acknowledgments
This research was supported by the National Natural Science
Foundation of China (no. 21073163), the National High Technology Research and Development Program of China (863 Program)
(no. 2011AA060907), and the Zhejiang Provincial Natural Science
Foundation, China (no. Z4110186).
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