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Bioresource Technology 102 (2011) 9335–9344

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Review

Recent progress in electrodes for microbial fuel cells


Jincheng Wei, Peng Liang, Xia Huang ⇑
State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, PR China

a r t i c l e i n f o a b s t r a c t

Article history: The performance and cost of electrodes are the most important aspects in the design of microbial fuel cell
Received 10 May 2011 (MFC) reactors. A wide range of electrode materials and configurations have been tested and developed in
Received in revised form 6 July 2011 recent years to improve MFC performance and lower material cost. As well, anodic electrode surface
Accepted 9 July 2011
modifications have been widely used to improve bacterial adhesion and electron transfer from bacteria
Available online 19 July 2011
to the electrode surface. In this paper, a review of recent advances in electrode material and a configura-
tion of both the anode and cathode in MFCs are provided. The advantages and drawbacks of these elec-
Keywords:
trodes, in terms of their conductivity, surface properties, biocompatibility, and cost are analyzed, and the
Microbial fuel cells
Electrode materials
modification methods for the anodic electrode are summarized. Finally, to achieve improvements and the
Electrode configuration commercial use of MFCs, the challenges and prospects of future electrode development are briefly
Electrode surface modification discussed.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction surface roughness, good biocompatibility, and efficient electron


transfer between bacteria and electrode surface, are essential for
Microbial fuel cell (MFC) technology is a prospective technology high bio-catalytic activity. In order to improve bacterial adhesion
that purifies wastewater and converts its chemical energy into and electron transfer, electrode surface modification has become
electrical energy using bacteria as catalysts (Logan et al., 2006). a new topic of interest in the research field of MFCs. The electrode
Even with the remarkable improvements in power density, the material for air–cathodes with a catalyst is composed of a base
large-scale application of MFCs has yet to be implemented due to material, a catalyst, a binder, and a waterproof coating. Material
low yields of power generation and high costs. Electrode is the characteristics and functions are specific for each part. The base
key component in deciding the performance and cost of MFC. Elec- material generally only serves as supporting material and current
trode design is the greatest challenge in making MFCs a cost-effec- collector. High conductivity and mechanical strength are critical
tive and scalable technology (Rabaey et al., 2009). Recently, for it. But there is no special requirement for bacteria adhesion. A
interest in the electrode material and its configuration has steadily catalyst is important for air–cathodes, but not absolutely neces-
increased in studies for MFCs. Over the past decade, a variety of sary. If necessary, the catalyst is immobilized on the substrate
electrodes have been extensively explored for MFCs. These elec- surface with a binder, and a hydrophobic coating is regularly added
trodes can be classified into two main groups, bio-electrodes onto the cathode to avoid water loss. To reduce the cost of
(including anode and biocathode) and chemical-electrodes (more air–cathodes, several highly specific materials, such as activated
specifically, air–cathode and aqueous air–cathode), according to carbon, that do not require a catalyst have been developed and
whether or not bacteria is used as a catalyst. reported (Deng et al., 2010; Zhang et al., 2009a). For aqueous
The electrode materials in MFC have some general characters air–cathode, only base material, catalyst and binder are needed.
and also its self-characteristic. For all the types of electrodes, their Another great challenge in making MFCs a high performance
base materials must generally be of good conduction, good chem- and scalable technology is electrode configuration. Commonly
ical stability, high mechanical strength, and low cost. Carbon mate- used electrodes can be classified according to their configurations:
rials and non-corrosive metals, which can basically meet the the plane electrode and the three-dimensional electrode. A good
general requirements above, are currently the most-widely used configuration for bio-electrodes must provide a large surface area
base materials (Fig. 1). In addition, there are some specific require- for bacterial adhesion and ensure efficient current collection. Plane
ments for each group of electrodes. Bio-electrodes function not electrode is more common for air–electrode. When the air–elec-
only as a conductor, but also as a carrier of bacteria, and some trode contains a chemical catalyst, an effective configuration is
special surface characteristics of electrode materials, such as high necessary to ensure the oxygen reduction into a three-phase
reaction involving the catalyst, the air, and water (Logan, 2007).
⇑ Corresponding author. Tel.: +86 10 62772324; fax: +86 10 62771472. In this paper, recent advances in electrode materials and config-
E-mail address: xhuang@tsinghua.edu.cn (X. Huang). urations are explored. The advantages and disadvantages of the

0960-8524/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2011.07.019
9336 J. Wei et al. / Bioresource Technology 102 (2011) 9335–9344

performance of these commonly used anode materials are sum-


marized in Table 1. Photographs of these materials were shown
in Fig. 1. It is known that type and concentration of bacteria on
anodes is able to significantly affect power density (or current
density) in MFCs. Thus the inoculation sources were also summa-
rized in Table 1. It is shown that mixed culture, including acti-
vated sludge, domestic wastewater and preacclimated bacteria
from an active MFC (originally inoculated with activated sludge
or domestic wastewater), were most common used inoculums
in studies for anode materials. However, little research has been
done on the effect of inoculation source on power generation
and the effect of material characteristics on community structure
and biomass. Here, we can loosely think of the difference in
inoculation source slightly affected the comparison of anode
performance.

2.1. Carbonaceous anode

Carbonaceous materials are the most widely used materials for


MFC anodes because of their good biocompatibility, good chemical
stability, high conductivity, and relatively low cost. In terms of
configuration, carbon-based electrodes can be divided into a plane
structure, a packed structure, and a brush structure. The carbona-
ceous electrodes are discussed in detail in this section based on
this classification.

2.1.1. Plane structure


In the laboratory, carbon paper, graphite plates or sheets, and
carbon cloth are the most common materials for plain electrodes
(Min and Logan, 2004; Sun et al., 2010). Carbon paper is very thin
and relatively stiff but slightly brittle. Graphite plates or sheets
have higher strength than carbon paper. Roughened graphite elec-
trodes have been reported to produce a higher power density than
flat graphite electrodes (ter Heijne et al., 2008). These two materi-
als have a compact structure and a relatively smooth surface, both
of which facilitate the quantitative measurement of biomass per
unit of surface area. However, their low specific area and high cost
inhibit the application of these electrodes in large-scale MFCs. In
comparison with carbon sheets, carbon cloth is more flexible and
much more porous, allowing more surface area for bacterial
growth. However, it is prohibitively expensive to use for MFCs
(ca. $1000/m2) (Zhang et al., 2010). An inexpensive carbon mesh
material ($10–40/m2) was examined by Wang et al. (2009) as a
substantially less expensive alternative to carbon paper and carbon
cloth; results showed that the carbon mesh exhibited a slightly
higher power density than carbon cloth after both materials were
treated with ammonia gas. The comparison of untreated materials,
Fig. 1. Photographs of electrode materials used for MFC: (A) carbon paper; (B) however, was not reported. Besides the plain materials described
graphite plate; (C) carbon cloth; (D) carbon mesh; (E) granular graphite; (F) above, some rarely used fibrous materials, such as graphite foil,
granular activated carbon; (G) carbon felt; (H) reticulated vitrified carbon; (I)
carbon fiber veil, and activated carbon cloth, have also been re-
carbon brush; (J) stainless steel mesh.
ported and comparatively evaluated for sulfide electrochemical
oxidation in the anode of MFCs (Zhao et al., 2008). The results
electrodes are compared in terms of their characteristics, perfor- showed that the activated carbon cloth achieved the best sulfide
mance, cost, and application range, and the surface modification removal and power generation due to its high specific surface
methods of anode materials are summarized. The microorganisms and adsorption capacity.
used in the MFCs studies for anode and biocathode materials were Graphite or carbon felt is another fiber fabric that is much thick-
detailed in Tables. Finally, to realize the potential large-scale appli- er than the materials described above. Its loose texture confers
cation of MFCs, the main challenges and directions in electrode more space for bacterial growth than carbon cloth and graphite
development are discussed. sheets, but the growth of bacteria is more likely to be restricted
by the mass transfer of substrate and products on its inner surface.
In order to increase the available surface area for bacteria, the felt
2. Anode materials for MFCs is cut into cubes and placed into an anode chamber. Graphite foam
is yet another porous carbon-based material with a definite thick-
Common materials in laboratory MFCs include a large variety ness, but it is seldom used in MFCs. Chaudhuri and Lovley (2003)
of carbon materials and several metal materials, which vary compared the performance of graphite rod, felt, and foam based
greatly in configuration and surface area. The configuration and on the surface area of the resulting electrode. Similar currents
J. Wei et al. / Bioresource Technology 102 (2011) 9335–9344 9337

Table 1
Anode materials, configuration, inoculation source and power generation performance in MFC.

Electrode materials Configuration Electrode size Inoculation source Reactor configuration Maximum power or References
current density
Carbon Carbon Plane 2.5 cm  4.5 cm, Primary clarifier overflow Two-bottle, air– 600 mW/m2 (anode area) Logan
paper 22.5 cm2 total cathode et al.
(2007)
Carbon Carbon Plane 7 cm2 in projected area Preacclimated bacteria from an Single chamber cube 46 W/m3 (anode chamber Zhang
cloth active MFC air–cathode MFCs volume) et al.
(2009b)
Carbon Graphite Plane 1.92 cm2 Shewanella oneidensis (MR-1) Two chamber, 3290 mW/m2 (anode Dewan
plate air–cathode area) et al.
(2008)
Carbon Graphite Plane 155 cm2 Shewanella oneidensis (MR-1) Two chamber, 1410 mW/m2 (anode Dewan
plate air–cathode area) et al.
(2008)
Carbon Carbon Plane 7 cm2 in projected area Preacclimated bacteria from an Single chamber cube 893 mW/m2 (anode area), Wang
mesh active MFC air–cathode MFC 45 W/m3 (anode chamber et al.
volume) (2009)
Carbon Activated Plane 1.5 cm2 in projected D. desulfuricans strain Essex 6 Single chamber, 0.51 mW/cm2 (geometric Zhao et al.
carbon area (for sulfate removal) air–cathode MFCs electrode area) (2008)
cloth
Carbon Granular Packed Granular diameters: Preacclimated bacteria from an Tubular MFC, 90 W/m3 (net anodic Rabaey
graphite 1.5–5 mm; anode active MFC catholyte: K3Fe(CN)6 chamber volume) et al.
chamber: 390 mL (2005)
Carbon Graphite Packed Anode chamber: Preacclimated bacteria from an Two chamber MFC, 386 W/m3 (anode Aelterman
felt 156 mL active MFC catholyte: K3Fe(CN)6 chamber volume) et al.
(2008)
Carbon Carbon felt Packed Anode chamber: Preacclimated bacteria from an Two chamber MFC, 356 W/m3 (anode Aelterman
156 mL active MFC catholyte: K3Fe(CN)6 chamber volume) et al.
(2008)
Carbon Granular Packed Anode chamber: Domestic wastewater Single chamber 5 W/m3 (volume of anode Jiang and
activated 450 mL, wet volume: cylindrical MFC, chamber) Li (2009)
carbon 250 mL air–cathode
Carbon Reticulated Packed Anode volume: 190 mL; Anaerobic sludge from a Two chamber 170 mW/m2 (anode He et al.
vitreous anode surface area: anaerobic bioreactor treating cylindrical MFC; surface area) (2005)
carbon 97 cm2 brewery wastewater K3Fe(CN)6 catholyte
Carbon Carbon Brush 4 cm long by 3 cm in Preacclimated bacteria from an Single chamber cube 2400 mW/m2 (cathode Logan
brush diameter active MFC air–cathode MFC, area), or 73 W/m3 et al.
batch-fed (2007)
Metal Stainless Plane 20  30 cm, total Marine sediments Artificial marine MFC 23 mW/m2 (anode Dumas
steel plate surface area 0.12 m2 surface area) et al.
(2007)
Metal Pt-coated Plane Projected area: 22 cm2 Preacclimated bacteria from an Two chamber Unreported ter Heijne
titanium active MFC (plexiglass plates et al.
with flow channels) (2008)

and biomasses were obtained from graphite rod and felt elec- 2010; Li et al., 2010; Rabaey et al., 2005). Similar to the biological
trodes, and the graphite foam electrode produced 2.4 times more filter, the anode chamber of the MFC can be filled with granular or
current density and 2.7 times more cell density than the graphite irregularly shaped packing. However, the granular packing mate-
rod one. Several studies on reticulated vitrified carbon (RVC), a sig- rial, such as granular graphite, must be conductive. Graphite rods
nificantly porous (97%), conductive (5  10 3 X cm), and rigid but are usually used to collect electrons in laboratory-scale MFCs.
brittle material, as an anode have been conducted (He et al., 2005; Having a high specific area is the main advantage of this configura-
Ringeisen et al., 2006; Scott et al., 2008a,b). The specific surface tion. The specific area of granular graphite (1.5–5.5 mm diameter)
area of RVC was found to be 51 and 6070 m2/m3 in studies by He used in MFCs was estimated to be between 817 and 2720 m2/m3
et al. (2005) and Ringeisen et al. (2006), respectively. Similar to (Rabaey et al., 2005). In order to make the complete bed conduc-
graphite felt, RVC can be used as packing material with which to tive, the granules must be tightly packed next to each other,
fill the anode chamber. although dead zones for current collection may still exist after long
Most MFC studies involving the materials mentioned above term running (Logan, 2007). In addition, the porosities of the
only focus on maximizing power densities on a volume or mem- packed electrode are relatively low (only ranged from 30% to 50%
brane area basis, and few studies have reported on normalized for granular media), and thus, potential clogging after long-term
power densities at the surface area of the electrode, resulting in running is another problem (Rabaey et al., 2009). The use of gran-
difficulties in quantitative comparisons among different materials. ular graphite as an anode material in packed bed MFCs was first
More porous anode materials typically produce more power per reported by Rabaey et al. (2005). Granular activated carbon
geometric surface area compared to their smooth counterparts. (GAC) and small cubes of graphite or carbon felt can also be used
This is mainly due to the larger surface area available to bacteria as materials for packing bed MFCs. Aelterman et al. (2008) com-
per unit volume of anode chamber of porous anode materials. pared graphite and carbon felt, and 2 and 5 mm graphite granules,
and found that the graphite felt electrode yielded the highest max-
2.1.2. Packed structure imum power output, amounting to up to 386 W/m3 in the total
To increase the surface area available to bacteria, the use of car- anode compartment. Li et al. (2010) reported that a membrane-less
bon-based electrodes in packing forms for MFCs anode is becoming MFC, using GAC as the electrode, had a power density 2.5 times
increasingly common (Aelterman et al., 2008; Di Lorenzo et al., higher than an MFC that used carbon cloth. They thus inferred that
9338 J. Wei et al. / Bioresource Technology 102 (2011) 9335–9344

the high surface area of GAC significantly improves bacterial adhe- 2.3. Surface treatments and coatings for the anode materials
sion and electron transfer from bacteria to the GAC surfaces.
As mentioned above, the surface characteristic of anode materi-
als is one of the deciding factors that affect bacterial attachment
2.1.3. Brush structure and electrical connections between bacteria and the electrode sur-
The graphite brush anode is an ideal electrode that achieves face. Recently, modification of the anode using different materials,
high surface area, high porosities, and efficient current collection. which can be expected to facilitate bacterial adhesion and electron
The use of a brush anode was first reported by Logan et al. transfer to the anode surface, has been a successful approach for
(2007). In their studies, the brushes were made of carbon fibers improving power production in studies for MFCs. These modifica-
cut to a set length and wound into a twisted core consisting of tion methods include (i) surface treatments with physical or chem-
two conductive but noncorrosive titanium wires. Two brush sizes ical methods, (ii) addition of highly conductive or electroactive
were used in this study: the smaller brush, about 2.5 cm in diam- coatings, and (iii) use of metal–graphite composite electrodes are
eter and 2.5 cm long, had an estimated surface area of 18,200 m2/ summarized according to their performance improvements on
m3-brush volume and 95% porosity, while the larger brush, about MFC in Table 2.
5 cm in diameter and 7 cm long, produced 7170 m2/m3-brush
volume and 98% porosity. The cube MFCs containing the smaller 2.3.1. Surface treatment methods
brush reached a maximum power density of 2400 mW/m2 (nor- One of the successful surface treatments recorded in earlier
malized to the cathode projected surface area), and a maximum reports was achieved by treating a carbon cloth using 5% NH3 gas
Coulombic efficiency (CE) of 60%. Bottle MFCs with the larger brush in a helium carrier gas at 700 °C, which increased power from
anode produced a maximum power density of 1430 mW/m2, 1640 to 1970 mW/m2 and reduced the start-up time by 50% (Cheng
versus a 600 mW/m2 plain carbon paper anode. The performance and Logan, 2007). This improvement due to the increase of the
of brushes with different masses of fibers were also tested, but positive surface charge of the cloth from 0.38 to 3.99 meq/m2,
the lack of a clear trend in power per mass loading suggested that and this increase in positive surface charge favor the formation
the clumping of fibers was a problem that hindered bacterial of biofilm. Wang et al. (2009) reported a more environment-
access to the fiber surfaces, as well as the diffusion of substrate into friendly and economic method of improving power production in
the brush interior (Logan, 2007). MFCs. This method involved heating the carbon mesh in a muffle
furnace at 450 °C for 30 min, resulting in a 3% increase in maxi-
mum power density. Surface oxidation of carbon materials can also
2.2. Metal and metal oxide anode be an effective treatment method. Acid soaking of carbon fiber
brushes using concentrated sulfuric acid increased power by 8%,
Metal materials are much more conductive than carbon materi- and the combined acid and heat anode treatments further
als, but they are not widely applicable as carbon materials in MFCs. increased power by 25% (Feng et al., 2010). The improvement in
Many metals were ruled out because of the non-corrosive require- power generation with the acid and heat treated anode could
ment for anode materials. So far, only stainless steel and titanium result from three different factors: (i) Increase in specific area
have qualified as relative common base materials for anodes. Some (from 7.11 to 43.9 m2/g) facilitates bacteria adhesion on electrode.
of the metal-decorated anodes will be summarized in a later sec- (ii) Higher ratio of protonated N to the total N gives more positive
tion of this paper. charge on electrode surface, which also favors bacteria adhesion.
Generally, the smooth surface of metals does not facilitate the (iii) Lower C–O composition on acid and heat treated anode surface
adhesion of bacteria. As to be seen in the succeeding sections, some may indicate less of contaminants that interfere with charge trans-
non-corrosive materials, such as stainless steel, fail to achieve fer from bacteria to anode surface (Wang et al., 2009).
higher power densities compared with carbon materials. Dumas Lowy and Tender (2008) reported that the kinetic activities of
et al. (2007) tested the suitability of a stainless steel plate as both graphite plate anode increased 58.8 times compared to untreated
the anode and biocathode electrodes in an MFC, and found that the anode through electrochemical oxidation pretreatment at +1.85 V
power density (23 mW/m2) was limited by the anode. In another vs. Ag/AgCl. Similarly, Tang et al. (2011) discovered that a graphite
study, Dumas et al. (2008a) found that the stainless steel anode felt anode produced 39.5% higher current than an untreated anode
was less efficient than the graphite one. In contrast, Erable and after electrochemical oxidization at a constant current density of
Bergel (2009) found that the stainless steel grid anode produced 30 mA/cm2 for 12 h. The authors thus inferred that electrochemical
much higher current densities than plain graphite ones when a treatment of graphite felts generates carboxyl-containing func-
constant potential ( 0.1 V vs. the saturated calomel electrode) tional groups on the surface of the anode. These groups facilitate
was applied to them. These results, however, may be reversed the electron transfer from bacteria to electrode, due to their strong
when current densities are normalized to the electrode surface. hydrogen bonding with peptide bonds in bacterial cytochromes.
Titanium is another commonly used metal material for MFC
anodes. As mentioned above, titanium, such as titanium wires in 2.3.2. Coatings
a graphite brush, is regularly used as a current collector. ter Heijne Aside from surface treatments, other approaches have been ta-
et al. (2008) compared titanium and graphite in terms of their ken to increase anode performance via the addition of a surface
suitability as an anode in MFCs. Their results showed that the coating. The surface coating materials currently reported include
anode performance decreased in the following order: roughened carbon nanotubes (CNTs), conductive polymers, mediators, metals,
graphite > Pt-coated titanium > flat graphite > uncoated titanium. and composites of these materials.
No current was observed for the uncoated titanium anode. For The most commonly used material is CNT or metal anchored
the three other materials, the specific surface area and biomass CNT, which has been proven to be efficient for improvements in
activity were important variables in explaining the differences in power generation (Liang et al., 2011; Peng et al., 2010; Sharma
current density between them. et al., 2008; Sun et al., 2010; Tsai et al., 2009; Yuan et al., 2009).
Gold anodes have also been used in several studies (Crittenden Using electrochemical methods, such as cyclic voltammetry and
et al., 2006; Richter et al., 2008). Richter et al. (2008) found that electrochemical impedance spectroscopy, several studies revealed
Geobacter sulfurreducens could grow on gold anodes, producing that CNTs can facilitate electron transfer from bacteria to electrode
currents nearly as effectively as in graphite anodes. and thus, reduce the internal resistance of MFCs (Peng et al., 2010;
J. Wei et al. / Bioresource Technology 102 (2011) 9335–9344 9339

Table 2
Methods of anode modification, inoculation source and the improvements in performance of MFCs.

Materials and methods Base material Inoculation source Improvement in References


performance
Surface treatment NH3 gas treatment Carbon clothes Domestic wastewater Increase power density by Cheng and Logan (2007)
20%, reduce start-up time
by 50%
Surface treatment Heat treatment Carbon mesh Preacclimated bacteria from Increase power density by Wang et al. (2009)
an active MFC 3%
Surface treatment Heat treatment Carbon brush Domestic wastewater Increase power density by Feng et al. (2010)
25%
Surface treatment Acid (H2SO4) treatment Carbon brush Domestic wastewater Increase power density by Feng et al. (2010)
8%
Surface treatment Acid (HNO3) treatment Graphite felt Brewery wastewater 2-Fold increase in power Scott et al. (2007)
diluted with domestic density
wastewater (1:100 by
volume)
Surface treatment Heat and acid treatment Carbon brush Domestic wastewater Increase power density by Feng et al. (2010)
25%
Surface treatment Electrochemical oxidation Graphite felt Preacclimated bacteria from Increase current density by Tang et al. (2011)
an active MFC 39.5%
Surface treatment Electrochemical oxidation Graphite plates Marine sediments 56.8-Fold increase in kinetic Lowy and Tender (2008)
activities
Surface coating Carbon nanotube Carbon paper Mixed-culture anaerobic Increase power density by Sun et al. (2010)
granular sludge 20%
Surface coating Carbon nanotube Carbon clothes Domestic wastewater 0.7–30.5-Fold increase in Tsai et al. (2009)
power density for different
types of reactors
Surface coating Carbon nanotube Glassy carbon Shewanella oneidensis MR-1 82-fold increase in current Peng et al. (2010)
density
Surface coating Polypyrrole coated carbon Carbon paper Escherichia coli (DH5a Maximum power density Zou et al. (2008)
nanotubes composite strain) 228 mW/m2
Surface coating Pt decorated carbon Carbon paper Escherichia coli (DH5a 6-Fold increase in the Sharma et al. (2008)
nanotube strain) power density
Surface coating Polyaniline Graphite felt Brewery wastewater 1.8-Fold increase in power Scott et al. (2007)
diluted with domestic density
wastewater (1:100 by
volume)
Surface coating AQDS Graphite disk Marine sediments 0.7-Fold increase in kinetic Lowy et al. (2006)
activity
Surface coating NQ Graphite disk Marine sediments 0.5-Fold increase in kinetic Lowy et al. (2006)
activity
Surface coating NR Graphite felt Shewanella putrefaciens 54–454-Fold increase in Park and Zeikus (2002)
current density
Surface coating NR Graphite plates Domestic wastewater Power density reached Wang et al. (2011)
900 mW/m2
Surface coating Au nanoparticle Graphite disk Shewanella oneidensis MR-1 20-Fold increase in current Fan et al. (2011)
density
Surface coating Pd nanoparticle Graphite disk Shewanella oneidensis MR-1 Increase current density by Fan et al. (2011)
50–150%
Surface coating Iron oxide Carbon paper Anaerobic sludge 2.75-Fold increase in the Kim et al. (2005)
power density
Surface coating Graphite paste containing Graphite disk Marine sediments 1.1-Fold increase in kinetic Lowy et al. (2006)
Fe3O4 activity
Surface coating Graphite paste containing Graphite disk Marine sediments 0.7-Fold increase in kinetic Lowy et al. (2006)
Fe3O4 and Ni2+ activity
Composite electrode Sb(V) complex in graphite – Marine sediments 0.9-Fold increase in kinetic Lowy and Tender (2008)
paste activity
Composite electrode Mn2+ graphite – Shewanella putrefaciens 78–509-Fold increase in Park and Zeikus (2002)
current density
Composite electrode Graphite-ceramic – Marine sediments 1.2-Fold increase in kinetic Lowy et al. (2006)
containing Mn2+ and Ni2+ activity

Sun et al., 2010). It is known that nanomaterials can inactivate or outperformed CNT/conductive polymers alone (Scott et al., 2007;
kill bacteria, thus further investigation of the negative effects of Zou et al., 2008).
nanomaterials on bacteria metabolism and essential reasons of In many earlier studies, a variety of mediators, for example,
the promotion in power generation are still needed. neutral red (NR), anthraquinone-1,6-disulfonic acid (AQDS), and
The addition of conductive polymers, such as PANI and polypyr- 1,4-naphthoquinone (NQ), were used to facilitate the shuttling of
role, to the anode surface has also been tested on MFCs (Jiang and electrons from inside the cell to the electrodes outside the cell.
Li, 2009; Zhao et al., 2010). The increase in current densities However, all these mediators must be continually added or recy-
presumably resulted from the increased surface area and enhanced cled. This problem can be solved by immobilizing the electron
electron collection of the anode. Supplementary work has also mediator on the electrode surface. Mediators immobilized on
been done on the addition of a CNT/conductive polymer composite graphite anodes have been shown to significantly increase power
to anodes, and the results indicate that the composite coating in several studies (Lowy and Tender, 2008; Lowy et al., 2006; Park
9340 J. Wei et al. / Bioresource Technology 102 (2011) 9335–9344

and Zeikus, 2003; Wang et al., 2011). However, the immobilized supporting material, and a catalyst/binder layer (exposed to
mediators could be deactivated due to drop out or degraded during water). Aqueous air–cathodes are made of conductive supporting
long-term operation. Thus, the stability of this modified electrode materials, such as carbon paper, carbon cloth, and platinum mesh,
needs to be confirmed in practice. coated with a catalyst/binder layer (Logan et al., 2005; Scott et al.,
Metal and metal oxidation-coated anodes have also been re- 2008b; Yu et al., 2007). However, the solubility of oxygen (mole
ported in several studies. In microbial electrochemical cells, Fan fraction basis) in water is only 4.6  10 6 (25 °C) compared to
et al. (2011) decorated graphite with Au nanoparticles. The result- 0.21 in air (Logan, 2007), so the performance of aqueous air–cath-
ing anode provided current densities 20 times higher than plain odes is limited by their low concentration of dissolved oxygen. Air–
graphite were used as anode. Pd-decorated anodes made with sim- cathodes are believed to be a more practical design for MFC cath-
ilar methods only produced current densities 1.5–2.5 times higher odes, and they have attracted much more attention than other
than the control. In one study, Kim et al. (2005) reported that iron cathodes because they require no aeration and generate higher
oxide-coated anodes improved biocompatibility, and thus pro- power densities. The materials for air–cathodes will be provided
duced higher power densities and Coulombic efficiency (CE), com- in detail in this section.
pared with plain anodes. Similarly, Lowy et al. (2006) found that Similar to anode materials, the use of carbon-based electrodes
graphite modified with a graphite paste containing Fe3O4 or in cloth forms as a supporting material is very common for
Fe3O4 and Ni2+ possessed between 1.5–2.2 times greater kinetic air–cathodes (Cheng et al., 2006a,b; Logan et al., 2007). Compared
activity than plain graphite. with carbon paper and carbon cloth, more economical and practi-
cal air–cathodes that use stainless steel as the supporting material
2.3.3. Composite electrodes have been developed by several researchers. Zhang et al. (2010)
The performance of self-made metal–graphite composite an- constructed a cathode around the metal mesh itself, and You
odes has been tested in several studies. Using an Mn4+-graphite et al. (2011) reported the fabrication of a new membrane electrode
electrode made by mixing manganese sulfate with fine graphite assembly air–cathode by using stainless steel mesh as a raw
powder, the amount of electrical energy produced can increase material. This cathode achieved a power density similar to an
1000-fold (Park and Zeikus, 2002). Here, Mn4+ was used as a medi- air–cathode based on carbon cloth.
ator linked to graphite electrodes. Lowy and Tender (2008) re- When a catalyst is used on a cathode, it is typically bound to the
ported that the kinetic activity of an anode made by mixing a electrode substrate using a polymer. Perfluorosulfonic acid (Naf-
sulfide-oxidizing Sb (V) complex and graphite paste was 1.9 times ion) and poly(tetrafluoroethylene) (PTFE) are two commonly used
higher than that of a graphite paste anode. The Sb (V) complex usu- binders in MFCs. Cheng et al. (2006b) compared Nafion and PTFE to
ally functioned as a mediator in anode chamber. Thus it can effi- determine the effect of these binders on power densities in a single
ciently mediate electron transfer from bacteria to anode. In chamber air–cathode MFC. The MFC using Nafion binder produced
another study, a graphite–ceramic composite containing Mn2+ a higher maximum power density (400 ± 10–480 ± 20 mW/m2)
and Ni2+ was proven to be kinetically advantageous over plain than that using PTFE (331 ± 3–360 ± 10 mW/m2). The author gave
graphite (Lowy et al., 2006). Whether or not these increases in one possible reason that the biofilm formed on PTFE cathode was
power are due to the potentials of the metals or other reasons, thin and loose compared to that formed on Nafion cathode, and
however, requires further investigation. biofilm formation is a function of the hydrophobicity of the surface.
The studies mentioned above mainly focus on the improve- However, the relation between performance and the inherent
ments in power generation performance, but very little is known properties of binders need to be further investigated. It is worthy
about the mechanism for these upgrades. As a result, further inves- of note that Nafion can cost up to 500 times more than PTFE (mass
tigation may be needed to shed light on the mechanism of interac- basis) (Cheng et al., 2006b). Further investigations are recom-
tions between bacteria and the electrode surface in order to help mended to identify a new binder with high performance and low
advance the knowledge base needed for new anode designs. In cost.
addition, the cost-effectiveness of these modified anodes also To avoid high oxygen fluxes from outside to inside the reactor,
needs to be evaluated in terms of cost and long-term stability. as well as water losses through the air–cathode, a hydrophobic
coating layer (usually called diffusion layer) is needed on the air-
facing side of the cathode in a single chamber MFC. Cheng et al.
3. Cathode materials for MFCs (2006a) found that four PTFE diffusion layers was the optimum
number of coatings; this number of coatings resulted to a 171% in-
The performance of MFCs is currently limited by the cathode, crease in the CE and a 42% increase in the maximum power density
and this problem is projected to remain for some time (Logan, compared with a cathode without diffusion layers. Measurable
2009). Thus, cathode materials and their design are the most chal- water loss was prevented as well. Zhang et al. (2010) recently
lenging aspects of an MFC. Most of the materials mentioned above developed an inexpensive coating of poly(dimethylsiloxane)
used as the anode have also been used as the base materials of (PDMS) as a diffusion layer for stainless mesh air–cathodes. The
air–cathodes, aqueous air–cathodes, and bio-cathodes (Table 3). CE of the resulting mesh cathodes reached more than 80% and
The main difference in these materials used for the cathode is that water leakage was prevented.
a catalyst (i.e., Pt for oxygen reduction) is normally used but is not The distance across which proton transfer occurs from a mem-
always necessary (i.e., ferricyanide) (Logan, 2007). Except for the brane to a cathode is known to be positively correlated with the
advances in catalysts, which are not discussed here in detail ohmic resistance of cathode. In order to minimize the internal
due to the limited length of this paper, the development of cathode resistance of air–cathode MFCs, increasing membrane cathode
materials is summarized in the following section. assemblies (MACAs) were developed in recent years. In earlier
studies of MACAs (Liu and Logan, 2004; Min and Logan, 2004;
3.1. Air–cathodes and aqueous air–cathodes with catalysts Pham et al., 2005), the proton exchange membrane (PEM) was
hot pressed to the air–cathode. Kim et al. (2009b) optimized
Air–cathodes and aqueous air–cathodes with dissolved oxygen the fabrication conditions for MACAs made by platinum-catalyzed
are two of the most commonly used configurations for cathodes carbon cloth and cation exchange membranes (CEM), and discov-
for laboratory MFCs that require catalysts. The air–cathodes usu- ered optimal hot-pressing conditions with a temperature of
ally consist of a diffusion layer (exposed to air), a conductive 120 °C and pressure of 150 kg/cm2 for 30 s. Prakash et al. (2010)
Table 3
Cathode materials, configuration and performance in MFC.

Type Cathode materials Configuration Cathode size Catalyst MFC configuration Maximum power or current References
density
Air–cathode Carbon clothes, Nafion Plane 7 cm2 (projected surface Pt Single chamber cube MFC 400 ± 10–480 ± 20 mW/m2 Cheng et al. (2006b)
(binder), no diffusion area) (projected area of cathode)
layer
Air–cathode Carbon clothes, PTFE Plane 7 cm2 (projected surface Pt Single chamber cube MFC 331 ± 3–360 ± 10 mW/m2 Cheng et al. (2006b)
(binder), no diffusion area) (projected area of cathode)
layer
Air–cathode Carbon clothes, PTFE Plane 7 cm2 (projected surface Pt Single chamber cube MFC 766 mW/m2 (projected area of Cheng et al. (2006a)
(binder), PTFE (diffusion area) cathode)
layer)
Air–cathode Stainless Steel Mesh, Plane 7 cm2 (projected surface Pt Single chamber cube MFC 1610 ± 56 mW/m2 (projected Zhang et al. (2010)
Nafion (binder), area) area of cathode)
poly(dimethylsiloxane)
(diffusion layer)
Aqueous air–cathode Carbon paper Plane 2.5  4.5 cm Pt Two-bottle MFC 33 mW/m2 (anode area) Logan et al. (2005)

J. Wei et al. / Bioresource Technology 102 (2011) 9335–9344


Air–cathode without Activated carbon was Plane 7 cm2 (projected surface – Single chamber cube MFC 1220 mW/m2 (projected area Zhang et al.
catalyst cold-pressed with a PTFE area) of cathode) (2009a,b)
binder around a Ni mesh
Aqueous air–cathode Granular graphite with Packed Anode chamber: 350 mL, – Two chamber MFC 50 W/m3 (cathode liquid Freguia et al. (2007)
without catalyst nanoscale pores on it granular diameter <1 mm volume)
Aqueous air–cathode Nitric acid and thermal Packed Anode chamber: 50 mL – Cylindrical two chamber 8.1 W/m3 (net cathode Erable et al. (2009)
without catalyst activated graphite MFC chamber volume)
granules
Aqueous air–cathode Activated carbon fiber felt Plane Thickness: 5 cm, – Cylindrical two chamber 315 mW/m2 (cross-sectional Deng et al. (2010)
without catalyst projected surface area: MFC area of separator)
36 cm2
Aqueous air–cathode A mixture of ferric sulfate, Plane 20  20 cm – Single chamber MFC 788 mW/m2 (surface area of Park and Zeikus
without catalyst fine graphite powder, electrode) (2003)
kaolin and nickel chloride
MACA PEM carbon clothes Plane 7 cm2 (projected surface Pt Single chamber MFC 262 ± 10 mW/m2 (projected Liu and Logan
cathode assemblies area) area of cathode) (2004)
MACA Ultrafiltration (UF) Tubular 54 cm2 (cathode surface CoTMPP Single chamber MFC 18 W/m3 (total reactor Zuo et al. (2007)
membrane coated with area) volume)
graphite coating and
catalyst
MACA AEM or CEM coated with Plane 7 cm2 (projected surface CoTMPP Single chamber MFC 449 ± 35 and 286 ± 30 mW/m2 Zuo et al. (2008)
graphite coating and area) (projected area of cathode) for
catalyst AEM and CEM, respectively
MACA Canvas cloth coated with Tubular 14.5  17.5 cm MnO2 Tubular single-chamber Ni: 86.03 mW/m2; graphite Zhuang et al. (2009)
the mixture of Ni-based MFC based coating: 24.67 mW/m2
(or graphite-based) (projected cathode surface
conductive paints and area)
MnO2
Bio-cathode Granular graphite Packed Granular diameters: 1.5– Mixture of sediment, Tubular MFC with an 8 W/m3 (cathode liquid Clauwaert et al.
5 mm; cathode chamber: aerobic and anaerobic internal cathode volume) (2007a)
444 mL sludge
Bio-cathode Graphite felts Tubular Cathode chamber: 40 mL Mixture of sediment, Cylindrical two chamber 83 ± 11 W/m3 (total MFC Clauwaert et al.
(electrochemically aerobic and anaerobic MFC with a internal anode volume) (2007b)
pretreated to contain sludge chamber
manganese oxide)
Bio-cathode Graphite fibre brush Brush Unreported Aerobic sludge Two chamber MFC 68.4 W/m3 (anodic wet You et al. (2009)
volume)

9341
9342 J. Wei et al. / Bioresource Technology 102 (2011) 9335–9344

replaced the ion exchange membrane in MACAs with an inexpen- alone. Similarly, Duteanu et al. (2010) compared the oxygen reduc-
sive polyvinylidene fluoride and polystyrene sulfonic acid mem- tion activity of carbon powder modified with various chemicals,
brane. Similar maximum power densities were obtained for the including HNO3, H3PO4, KOH, and H2O2, in air–cathode MFCs. The
two MACAs made with different membranes. Another reported HNO3-treated carbon powder demonstrated the highest current
fabrication method is the application of a hydrogel between the densities (1115 mA/m2, at 5.6 mV), greater than those of a Pt-sup-
ion exchange membrane and the carbon cloth air cathode, which ported untreated carbon cathode.
increased the cathode potential by about 100 mV over a 0–5.5 mA Overall, activated carbon and HNO3-treated carbon powder
range (Kim et al., 2009a). This is because the hydrogel increases achieve higher power generation performance than other materials
the hydration of the cathode and the contact area between the used in catalyst free air–cathode. And they also outperformed
cathode and the membrane. Pt-supported air–cathode. The development of these inexpensive
A newly reported fabrication method for MACAs is to coat gas- materials significantly increases the cost-performance ratio of
permeable membranes or fabric with conductive paints and a cat- air–cathode.
alyst. Zuo et al. (2007) developed a tubular MACA by coating a
tubular ultrafiltration membrane (UFM) with graphite paint and 3.3. Biocathode
non-precious metal catalyst. For the MFC reactors with the same
volume, this tubular architecture provided much larger surface Biocathode have the important advantage of relatively low cost,
areas for oxygen reduction, and thus, higher power densities than good stability and multiple functions for wastewater treatment
the plain cathode. Zuo et al. (2008) then replaced UFM with a low- and biosynthesis. Thus it has become a rapidly emerging research
cost anion exchange membrane (AEM) and CEM, and found that topic within the MFC field (Huang et al., 2011). As mentioned
the AEM cathode with a conductive coating facing the solution per- above, the same materials are often used for the biocathode and
formed better than the CEM and UFM cathode in single-chamber anode in MFCs. Currently, biocathode electrodes are mainly com-
MFCs. Zhuang et al. (2009) constructed a lower cost membrane- posed of carbon-based materials, such as graphite plate, carbon
less cloth cathode assembly (CCA) by coating a canvas cloth with felt, granular graphite, and graphite fiber brush, as well as stainless
nickel-based or graphite-based paint and MnO2. Under the fed- steel mesh (Behera et al., 2010; Clauwaert et al., 2007a,b; Dumas
batch mode, Ni–CCA and graphite–CCA generated maximum et al., 2008b; Liang et al., 2009; Xie et al., 2011; You et al., 2009).
power densities of 86.03 and 24.67 mW/m2 (normalized to the The surface characteristics and surface area available for bacteria,
projected cathode surface area) in tubular MFCs, respectively. De- which depend on the nature of the electrode materials and their
spite their comparable performance, such CCAs cost less than 5% configuration, are two main factors that affect the biomass on
of the MACAs mentioned above. bio-cathodes and their performance (Huang et al., 2011). Dumas
et al. (2008b) reported that stainless steel performed better than
3.2. Air–cathodes and aqueous air–cathodes without catalysts graphite in supporting biocathodes when the reactor was inocu-
lated with G. sulfurreducens and the electrodes were polarized at
The use of Pt in air–cathodes and aqueous air–cathodes signifi- 0.60 V vs. Ag/AgCl. De Schamphelaire et al. (2010) found that car-
cantly increased the cathode cost. The price of cathode materials bon felt was more suitable than stainless mesh for biocathodes.
can account for the greatest percentage (47%) of capital costs of However, these comparisons of current and power density were
air–cathode MFCs (Rozendal et al., 2008). Many researchers have not normalized to the surface area of the electrode. Hence, the
pursued the possibility of using high specific area carbon materials material more suitable for biocathodes remains unconfirmed.
to reduce the cathodic reaction overpotential, rather than utilizing Packed and brush structures are accepted to be superior compared
catalysts. A non-catalyzed aqueous air–cathode made of granular with others because they provide larger surface areas for the con-
graphite achieved a power output up to 50 W/m3 (cathode liquid figuration of biocathodes. From a cost point of view remains a need
volume) due to the nanoscale pores on it (Freguia et al., 2007). for lower-costing electrode materials for practical application.
The use of non-catalyzed granular graphite as aqueous air–cathode
material was also reported by Tran et al. (2010). Compared with
graphite, activated carbon is a more ideal material for non-cata- 4. Challenge and outlook
lyzed air–cathodes. In the study of Zhang et al. (2009a), activated
carbon was cold-pressed with a PTFE binder to form the cathode The real goal of MFC designs is to achieve practical implemen-
around a Ni mesh current collector. This air–cathode produced a tation in a wastewater treatment system. Thus, scale-up is an
higher maximum power density (1220 mW/m2, normalized to important issue in MFC design. The main challenges for commer-
the cathode projected surface area) than a Pt-catalyzed carbon cializing scalable MFCs include the development of cost-effective
cloth cathode (1060 mW/m2). Deng et al. (2010) reported the materials and architectures that can be used in larger scale
application of an activated carbon fiber felt air–cathode in an up applications.
flow MFC; this cathode produced a maximum power density of
315 mW/m2 compared with a platinum-coated carbon paper one, 4.1. Electrode configuration
which produced lower values (124 mW/m2, 0.2 mg-Pt/cm2).
Electrode modification is another method of increasing the oxy- For the anode and bio-cathode of large-scale MFCs, large acces-
gen reduction activity of common carbon materials. In an aqueous sible surface areas for bacteria and efficient current collection are
air–cathode, Erable et al. (2009) discovered that the use of nitric essential to achieve high power density.
acid and thermal-activated graphite granules cathode led to a high Thus far, packed and brush structures are two relatively ideal
open circuit voltage of 1050 mV, which was associated with the in- configurations that can achieve high surface area for bacterial
crease of material surface and the emergence of nitrogen superfi- adhesion. Compared with a packed structure electrode, the high
cial groups on its surface. Air–cathode can also be made with porosities of brush electrodes can effectively avoid the potential
modified carbon materials. Park and Zeikus (2003) fabricated an for clogging. However, clumping fibers are a potential problem that
Fe3+-graphite air–cathode by mixing ferric sulfate with fine graph- decreases the effective area of fibers (Logan, 2007).
ite powder, kaolin, and nickel chloride. Because Fe3+ can act as The ohmic resistance of large-scale electrodes is a problem that
electron mediators on the cathode, the Fe3+–graphite cathode cannot be neglected. For example the electrical resistivity of graph-
showed superior performance compared with a graphite electrode ite is 1375 lX cm, compared with only 42 lX cm for titanium
J. Wei et al. / Bioresource Technology 102 (2011) 9335–9344 9343

Table 4 5. Conclusions
Cost and estimated bulk density of common electrode materials in MFC.

Electrode Material Material cost in Chinaa Electrode designs are the greatest challenge in manufacturing
configuration MFCs as a cost-effective technology. A variety of carbon and metal
Plane structure Carbon cloth 45–130 (¥/m2) materials have been explored to develop anodes and cathodes, and
Packed structure Graphite granule 5.5–20 (¥/kg) several electrode modification methods have been developed to
Packed structure Granular activated carbon 0.5–1 (¥/kg)
improve power generation. The electrode configuration has
Packed structure Carbon felt 150–300 (¥/kg)
Brush structure Carbon fiber 150–300 (¥/kg) evolved from a planar to a three-dimensional structure, However,
Plane structure Titanium 100–1000 (¥/m2) power generation and electrode cost discussed thus far have not
Plane structure Stainless steel mesh 7–50 (¥/m2) reached the levels for commercial use. Further studies on more
a
2010 values from http://www.alibaba.com/ and http://china.alibaba.com.
cost-efficient electrode materials and optimization of configura-
tions are expected to address these challenges and enhance the
corporation potential of large-scale MFCs with conventional waste-
water treatment systems.
(Rozendal et al., 2008). The resistance is known to be linearly re-
lated to the path length of the electron flow. Therefore, the electri-
cal resistivity of carbon materials is relatively high, which can Acknowledgements
produce high electrode ohmic losses in large-scale systems. In or-
der to decrease the ohmic resistance of large-scale electrodes, a This research was supported by National High Technology Re-
major concern that must be addressed in electrode configuration search and Development Program of China (863 Program) (No.
is the minimization of the travel distance of the electrons that have 2009AA06Z306).
to flow through electrode materials with low conductivity. Metal
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