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INTERNATIONAL JOURNAL OF ENERGY RESEARCH

Int. J. Energy Res. 2015; 39:543–556


Published online 11 December 2014 in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/er.3270

Energy harvest with mangrove benthic microbial fuel cells


Paule Salvin1, Olivier Ondel2, Christophe Roos1 and Florent Robert1,*,†
1
Laboratoire des Matériaux et des Molécules en Milieu Amazonien, Université des Antilles et de la Guyane, UAG-UMR ECOFOG,
F-97337 Cayenne, French Guiana
2
Université de Lyon, F-69622, Lyon, France, Université Lyon 1, Villeurbanne; CNRS, UMR 5005, Laboratoire Ampère, 43, Boulevard du
11 Novembre 1918, Villeurbanne, 69622, France

SUMMARY
Benthic microbial fuel cells (BMFCs) are continuous electricity generators using electroactive microorganisms and organic
matter from aquatic environment, respectively, as catalysts and substrate. In this paper, first a low-cost PVC-made structure
is constructed to harvest electricity from mangrove environment located in French Guiana. An in situ BMFC has given power
density of 30 mW/m2 of the anodic surface area. This performance has been confirmed by experience in laboratory where
inter-electrode distance and electrode surface area appeared to be power increasing factors. However, the output power of
one BMFC is not used to supply real devices such as autonomous sensors. Second, to meet this expectation, in parallel
and in series associations were considered. These associations were made in order to increase the output voltage and conse-
quently the power, to reach levels that can supply small sensors (about 3 V). Finally, to improve the performance of the series
association and to avoid the voltage reversal phenomenon, a voltage balancing circuit was simulated and added to the series
connections. With balancing method, the cell voltage of BMFCs can be equalized, and the performances can be improved.
This allows an optimal energy harvesting and a better global efficiency of the set. Copyright © 2014 John Wiley & Sons, Ltd.

KEY WORDS
balancing circuit; benthic microbial fuel cell; efficiency; energy harvesting

Correspondence
*Florent Robert, Laboratoire des Matériaux et des Molécules en Milieu Amazonien, Université des Antilles et de la Guyane, UAG-UMR
ECOFOG, F-97337 Cayenne, French Guiana.

E-mail: florent.robert@guyane.univ-ag.fr

Received 9 July 2014; Revised 29 September 2014; Accepted 20 October 2014

1. INTRODUCTION the overlaying water. BMFC is also operated in laboratory.


There, compartments are designed to contain sediments and
For a few years now, microbial fuel cell (MFC) has be- water collected from natural sites [9,10]. The main advantage
come of great interest as a future alternative in energy pro- of BMFC is its low cost of designing and functioning. Indeed:
duction. It is based on the catalysis of the electrochemical
reactions realized by electroactive biofilms (EAB), adhered i. Cheap materials, such as graphite, could be used to
on electrodes [1–3]. The anodic EAB catalyzes the oxida- build the electrodes, bacteria playing the role of
tion of the organic matter or the carbon source present in the catalyst [5];
the anodic chamber and transfers the generated electrons ii. Organic matter and inoculum are naturally present
to the conductive anode. Then, the difference of potentials in the chosen environment;
between the anode and the cathode induces that the electrons iii. No membrane is needed because the sedimentary
pass through an external circuit composed of generally resis- bacteria greatly consume oxygen, limiting its pres-
tive devices and go to the cathode where the reduction of the ence in the anodic part [11].
dioxygen or another oxidizer takes place [3].
One MFC design seems to be closer to a marketable pro- The mechanisms of current generation are multiple and
totype: benthic microbial fuel cell (BMFC) also called sedi- complex, associating abiotic and microbial reactions, but
ment microbial fuel cell (SMFC) [4]. Its name comes from also direct and indirect electronic transfers [12]. The average
benthic area where this kind of MFC is usually installed, power obtained from BMFC is 10–20 mW per anodic sur-
which is at the interface between sediments and water in face square meter, with maximal values of 109 mW/m2
aquatic environments (ocean, river, lake…) [5–8]. Anodes [13] and current density of 104 mA/m2 [14]. The perfor-
are embedded in sediments whereas cathodes are placed in mances are lesser than those announced for air-cathode

Copyright © 2014 John Wiley & Sons, Ltd. 543


P. Salvin et al. Microbial fuel cell

MFC (6.98 W/m2 for example, [15]) but the low cost, the medium to form bioanodes. In the present study, BMFCs
durability of the performance and the unlimited availability have been operated to harvest electricity from the same trop-
of the source of substrate are solid arguments to consider ical mangrove. With this design, no acetate or other electron
those results. Several explanations have already been ex- donors were needed to provide electricity as electron donors
posed concerning the limitations of the BMFC such as slow were naturally present in the sediments. In-situ- and
kinetics of the anodic and cathodic electrochemical reactions laboratory-located BMFCs have been tested, with consider-
and slow transfers of the reactants to both electrodes. ations on electrode spacing and electrode surface. Associa-
In the published studies on MFCs, increasing power was tions (in parallel or in series) of BMFC units have been
already performed thanks to parameter modifications such as considered as an adequate way to enhance power genera-
decreasing electrode spacing [9,16–18], increasing electrode tion. In this case, an electrical model was defined for each
surface [19–22] or reducing the membrane resistance [23]. BMFC in order to simulate the behavior of the various
Another improvement of the performance is brought by asso- associations. An electrical circuit has been added in order
ciations of numerous MFC units (e.g. stack operation or in to avoid the different constraints (voltage reversal, non-
parallel association) [24–27]. In the case of BMFC or SMFC, optimal efficiency) during the in series associations.
these combinations were not explored yet because of possi- Finally, the results obtained with in parallel and in series
ble limitations: first, connecting several cells in series could associations (with and without adding electrical circuit) are
not be possible in open systems such as aquatic environ- discussed.
ments [19,28] and second, overall potential could not be in-
creased in this configuration. To the best of our knowledge,
one research team has published about a self-stacked sub- 2. MATERIALS AND METHODS
mersible microbial fuel cell installed in lake sediments
[29]. They conceived an air-space for the cathodes connected 2.1. Benthic microbial fuel cells setup
by external tubes. Thus, cathodes were not in the same elec-
trolyte, and the voltages of the MFC could be cumulated. 2.1.1. General descriptions of the BMFCs
In a recent published study we have lightened the pres- BMFCs used in this study are based on a PVC-cylindrical-
ence of EAB in tropical mangrove sediments using electro- tube-made structure in form of an inverse (head at the bottom)
chemical cell as an electro-activity detector [30]. In this last letter F (Figure 1-A). Inside the structure, electrical junctions
case, acetate was provided as an electron source in the between titanium current collectors (titanium wires, 1.5-mm

Figure 1. A) Schematic representation of the in-situ BMFC placed in the mangrove. B) On the pontoon, the cell voltage is measured
thanks to a portative multimeter. C) Cubic glass-compartment containing the four laboratory-BMFCs. D) Laboratory BMFCs are con-
nected to electronic resistances placed in a plastic box. Pushing the red buttons opens or closes the electrical circuits.

544 Int. J. Energy Res. 2015; 39:543–556 © 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Microbial fuel cell P. Salvin et al.

diameter, Good Fellow) and copper cables are protected Ec-Lab v.10.12, Biologic SA). In the in-situ mangrove, a
from water. Outside of it, conductive electrodes are in con- portable multimeter is used, and the voltage is measured
tact with water and sediments at the bottom part. Indeed, the once a day. The current (I) is calculated according to
two parallel axes serve as inserts for the current collectors Ohm’s law (I = V / Rext) and then normalized by the
of both anode and cathode in order to maintain them in par- projected surface area of the anode to obtain the current
allel with anode in sediment and cathode in the overlaying density (J). Each BMFC is characterized by a polarization
water. Plastic gained copper cables immerged from water curve (V–I) obtained by the ‘Rext-variation’ procedure de-
to air at the upper part (above the main vertical axis). The scribed by Logan et al. [3]. A variable resistor box is used
latter link anode and cathode to a resistor (Rext) which to set external loads from 10 000 kΩ to 10 Ω (open-circuit
closes the electrical circuit. This output load is arbitrarily to short-circuit). The voltage for each load is taken after
set to 1 kΩ. Anode and cathode are both made with square pseudo-steady-state conditions have been established.
pieces of carbon cloth (carbon cloth, PaxiTech SA, France) The time needed varies between 5 and 30 min according
with a surface ratio of 1:1. to the difference between two consecutive values of Rext.
Power curve (P–I) is calculated from the polarization curve
2.1.2. In-situ BMFC and is a representation of power (P) versus current (I).
In this case, the BMFC is placed in the benthic zone of Evaluation of the internal resistance (Rint) of the cell is
an estuary mangrove (Figure 1-A). It is attached to a dock done by calculating the slope of the linear region of the
pontoon at 2 m below the water level at high tide. The re- polarization curve or calculating the resistance occurring
sistor is maintained on the dock, and it is never immersed at maximal power point: Rint ~ Pmax / I2.
in water (Figure 1-B). Over time, the cathode is always
in water (at high and low tides). The projected surface of
both electrodes, anode and cathode, is 72.25 cm2, and the 3. RESULTS AND DISCUSSION
distance between them is 12 cm.
3.1. Electrochemical results of the
2.1.3. Laboratory BMFCs individual BMFCs
Sediments and water sampled the same place areand
placed in a 70-L cubic compartment made in glass 3.1.1. BMFCs harvest electricity from natural
(Figure 1-C). Four BMFCs are fixed with metallic supports mangrove without substrate addition
and tongs which are outside and upper the compartment in 3.1.1.1. In-situ BMFC. The first aim of this study is
order to maintain the electrodes at the right level (anodes in to demonstrate that mangrove could be an adequate envi-
sediments and cathodes in water). The resistors are placed ronment to harvest electricity with a BMFC. Previous
in an electrical box where they are associated with electrical experiments showed that this environment constitutes an
switches, providing two operating modes: open circuit efficient inoculum to form bioanodes in three-electrode
(switch off equal to an infinite resistance) and closed circuit cells thanks to its salinity and its microbial community
(switch on—connected to a variable resistance) (Figure 1-D). [30]. BMFC appears to be a good way to test the ability
The BMFCs are named L1, L2, L3 and L4: L1 and L2 are rep- to generate electricity from the mangrove microbial activ-
licates with the same anode projected area (APA) 72.25 cm2 ity in real conditions. Our BMFC prototype stayed in place
and inter-electrode distance (IED) 12 cm. L3 has a lesser only 10 days in the mangrove because of the difficulties
APA of 56.25 cm2 but the same IED as L1. L4 has the same inherent to the chosen place (regular tides, presence of
APA as L1 but a lesser IED (5 cm). branches in water and strong estuary currents). During this
period, the voltage versus time curve (V–t curve) shows the
2.2. Mangrove water and sediments establishment of a difference of potential between the
anode and the cathode when the BMFC is connected to a
The mangrove located in the Larivot port area (Matoury, 1-kΩ resistor (Figure 2-A). Indeed, after 10 days of immer-
French Guiana) was a four-parameter sensor (HI9811-5, sion, the voltage reaches 453 mV. For logistical reasons,
Hanna Instruments) and the conductivity with inoculum the polarization curve and the power curve are realized af-
used in this study (water and sediments). The pH was mea- ter 7 days of immersion of the BMFC. The maximal power
sured in water samples with a conductivity meter (EC215, point (MPP) at this date (noted Pmax7) is 30 mW/m2 in water
Hanna Instruments) during both in-situ and laboratory ex- with pH 7.0 and conductivity of 17 mS/cm (Figure 2-B). The
periments. The pH varied between 7.0 and 7.6, and the voltage VMPP7 and current IMPP7 at MPP are, respectively,
conductivity varied between 3.9 mS/cm and 33.4 mS/cm 300 mV and 0.58 mA (current density JMPP = 110 mA/m2).
following the tides and the moment of the day. The internal resistance of the BMFC estimated from the
polarization curve is 500 Ω. These first results indicate that
2.3. Electrochemical measurements harvesting electricity from a natural environment such as
mangrove could be possible using a BMFC. The power
At the laboratory, the cell voltage (V) is continuously mea- curve, shown in Figure 2-B, has not been obtained at the
sured using a potentiostat as a voltmeter and recorded with maximal performance of the in-situ BMFC. Indeed, this
a data acquisition system (potentiostat VMP3—software value is obtained after 7 days of immersion. However, the

Int. J. Energy Res. 2015; 39:543–556 © 2014 John Wiley & Sons, Ltd. 545
DOI: 10.1002/er
P. Salvin et al. Microbial fuel cell

A Knowing the evolution law and knowing V1kΩ to 10 days


500
(parameter b), V500Ω can be determined at 10 days (noted
Cell voltage in mV
400 VMPP10) and Pmax10 inferred. Calculations are summarized
in Table I and give an estimated maximum power
300
Pmax10 = 54 mW/m2 after 10 days. Depending on the evolu-
200 tion of the voltage after 10 days, this power can be further
increased.
100 This performance could be very interesting if it was du-
rable in time because there are few studies which present a
0
0 2 4 6 8 10 performance equivalent in our conditions of work. Indeed,
Time in days in general, higher power densities (>30 mW/m2) are ob-
tained when improvements are made to get better electro-
B chemical reactions kinetics in the BMFC. For example,
500 40 the electrode material could be optimized adding catalysts
on cathode or increasing the anode surface [31–33]. Other
400
Cell voltage in mV

30 way, the concentration of reactants is increased near the

P in mW/m2
300
electrode as in Rezaei et al. experiments, with the addition
20 of chitin at the anode [9]. Reimers et al. recommended the
200 installation of their BMFC in an environment naturally
richer in organic substrate [34]. Nielsen et al. proposed a
10
100 new architecture for the BMFC with a benthic chamber
which concentrates the organic substrate around the anode
0 0
0 25 50 75 100 125 150
[35]. Recently, Song and Jiang showed that a pre-treatment
of the sediments by heat could increase the generation of
Current density in mA/m2
current [36].
Figure 2. In-situ BMFC characterization—A) Cell voltage in func-
tion of time. B) Polarization (white diamonds) and power density
(grey diamonds) curves after 7 days of immersion. 3.1.1.2. Laboratory BMFCs. After the test in real
conditions, the same experience is reproduced at the labo-
ratory, so that the problems linked to the in-situ BMFC are
establishment of cell voltage V1kΩ (Figure 2-A) shows that it avoided (tides, high currents, limited access…). Four
continues to increase almost linearly until the 10th day. So, BMFCs are placed in a compartment of 70 L and are
the maximal power density data of that BMFC would cer- named L1, L2, L3 and L4. L1 and L2 are similar with same
tainly be higher than 30 mW/m2. To have an approximate dimensions as the in-situ one. L3 has a smaller electrode
idea of the sustainable power after 10 days, from the polari- surface and L4 a shorter inter-electrode distance.
zation curve obtained, we assume a linear evolution of the During 30 days, the voltage of each BMFC (V1kΩ) in-
voltage versus time starting at day 7. The maximal power creases until it reaches a stable value (data not shown).
is calculated with Pmax = VMPP2/Rint (VMPP is obtained when This evolution could be attributed to the formation of the
Rext = Rint). Rint (equal to 500 Ω) was calculated from the po- biofilm at the surface of the electrode. Indeed, this link
larization curve. It remains to determine the cell voltage after between the growth of an electroactive biofilm and the
10 days with Rext = 500 Ω (noted VMPP10). For Rext = 500 Ω increase of the performance has already been shown [30].
and 1 kΩ, it is within the linear region of the polarization No supplementary organic substrate has been added in
curve (Figure 2-B). We can define the evolution law in this the compartment during the experiment. After 40 days of
area from this equation: V = a.ΔRext + b, with a the slope operation, the cell voltages continue to be stable while no
and b the value of V for Rext = 1 kΩ (noted V1kΩ). supplementary substrate has been ever provided to the
As the voltage evolution between 7th and 10th days system. So, these results demonstrate that the duration of
(Figure 2-A) is linear, we hypothesize that the polarization an in-situ BMFC could be more important if the system
curve after 10 days will have the same evolution in its could be resistant enough to the environmental and techni-
linear region. cal difficulties.

Table I. Maximal power determination after 10 days (Pmax10) by linear extrapolation.

Evolution law V1kΩ V500Ω(VMPP) Pmax(500Ω)


th 2
7 days a = 0.13 V = a. Rext + b 355 mV 290 mV 30 mW/m
b = 355
th 2
10 days a = 0.13 V = a. Rext + b 455 mV 390 mV 54 mW/m
b = 455

546 Int. J. Energy Res. 2015; 39:543–556 © 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Microbial fuel cell P. Salvin et al.

800
3.1.2. Electrode surface area and inter-electrode
distance enhance the power output

Cell voltage in mV
Laboratory BMFCs L1 and L2 are duplicates of the 600
in-situ BMFC (same anode surface area and same inter-
electrode distance). The analysis of their V–t curve 400
shows near close cell voltages’ values once the plate
value was achieved. At day 40, the cell voltages are
373 mV for L2 and 404 mV for L1. These voltages are 200
lower than those obtained with the in-situ BMFC despite
the same parameters of electrode surface and inter- 0
electrode distance. This lower performance could be 0.00 0.25 0.50 0.75 1.00 1.25
explained by the constant renewal of the media and the Current intensity in mA
reactants around the in-situ BMFC.
0.25
L3, with smaller electrodes’ surface area, presents the
lowest performance, i.e. 221 mV. This result indicates that
0.20
increasing the surface available for the microorganisms

Power in mW
could enhance the efficiency of the BMFC. L4, with a
0.15
reduced inter-electrode distance, reaches the highest maxi-
mum cell voltage, i.e. 471 mV. Reducing the gap between
0.10
the anode and the cathode seems to increase the cell volt-
ages, as detailed in introduction. This could be explained
0.05
by the decrease in the internal resistance of the BMFCs
through ion exchange facilities when the distance is shorter
0.00
between the electrodes. In the case of the in-situ BMFC, 0.00 0.25 0.50 0.75 1.00 1.25
ion exchange and redox reactions are certainly promoted Current intensity in mA
by the constant renewal of the environment brought by
tides phenomena (among others). In the case of laboratory Figure 3. Polarization curves (upper) and power curves (bottom) of
BMFCs, the lack of stirring of the medium, in particularly laboratory BMFCs. Mean values have been used for the duplicates
in the anodic part, could slow the reagent diffusion. More- L1 and L2 and red error bars are indicated on their curve. Circle
over, L4 has the closest performance to the 10 days in situ symbols are for L3 BMFC and cross symbols are for L4 BMFC.
BMFC’s one. However, this approach is not suitable for
the in-situ device due to the difficulty to control the sedi- 3.2. Increasing power via in parallel or/and
ment level at the interface sediment-water over time (peri- in series combinations of BMFCs
odical movement of the water).
The polarization curves and power curves of the labora- In regards of the application of BMFCs to supply real ap-
tory BMFCs, made in their stable phase, are shown in plication as wireless sensor for example, the power levels
Figure 3. All BMFCs have an open circuit voltage VOC described for the individuals laboratory BMFCs (between
which tends to range from 650 to 750 mV whereas the 300 and 400 mV for 1 kΩ) are not sufficient to supply an
short-circuit current varies between 0.2 mA (L3) and electronic device. In order to improve the voltage or cur-
1.2 mA (L4). This amplitude corresponds to that usually rent characteristics, the laboratory BMFCs are connected
found in the literature on BMFC [31]. Calculations of their either in parallel or in series. The differences between the
mean V, I and P values associated with standard deviation tests realized in situ and at the laboratory lead to test
have been realized for L1 and L2 BMFCs. They show that BMFCs under different conditions. From now on, we only
their comportment is quite similar in comparison with consider the results of the identically built BMFCs (i.e.
BMFCs L3 and L4 (Figure 3) as remarked with the V–t BMFC in situ, L1, L2). It was found that the internal
curve. The similarity is maximal in the linear region equivalent resistance (Rint) increases when fuel concentra-
between 485 and 300 mV of the polarization curve. The tion decreases. In this case, the voltage at maximum power
maximum power point MPP is the highest with 0.23 mW point VMPP is identical for reactors, while the MPP current
at 0.61 mA for L4 and the lowest for L3 with 0.08 mW at (IMPP) is different (Figure 4). For this reason, parallel asso-
0.20 mA (Figure 3 and Table II). Duplicates L1 and L2 ciation was preferred as a first step, in order to increase and
have a mean MPP of 0.154 ± 5.103 mW at 0.438 optimize the harvesting energy.
± 4.103 mA. The voltage corresponding to MPP (noted In fact, associating BMFCs in parallel allows to impose a
VMPP) for the duplicates L1 and L2 is 350 mV ± 6 mV. common voltage but with a different current through them.
VMPP for L3 and L4 are 400 mV and 370 mV (Figure 3 As we have seen (Figure 4) the cell voltage at the MPP
and Table II). Internal resistance Rint calculated from (VMPP) being almost identical for each BMFC. If this voltage
the slope in the linear region of the polarization curve, is imposed on each cell (in our case VMPP = 300 mV), then
respectively, for duplicates, L3 and L4 are 686 Ω, 1730 Ω they provide their maximum power. Thus the parallel associ-
and 510 Ω. ation will present the best energy efficiency.

Int. J. Energy Res. 2015; 39:543–556 © 2014 John Wiley & Sons, Ltd. 547
DOI: 10.1002/er
P. Salvin et al. Microbial fuel cell

Table II. Electrochemical characteristics corresponding to the maximal power Pmax of individual and in parallel associated laboratory
BMFCs.

BMFC names Theoretical


(individual or association L1–L2 in parallel Theoretical association L1–L2–L3–L4 in
associated) L1 L2 L3 L4 L1//L2 (experiment) L1//L2//L3//L4 parallel (experiment)

Voc in mV 659 710 663 647 – 664 – 653


Pmax in mW 0.15 0.16 0.08 0.23 0.31 0.28 0.62 0.56
VMPP in mV 315 310 400 370 310 290 310 330
IMPP in mA 0.46 0.52 0.2 0.61 0.98 0.96 1.79 1.67
Rint in Ω 700 680 1730 510 340 300 182 200

Thus all BMFCs are connected to a variable resistance Rext


(Figure 5-A). When the voltage is stable, Rext is varied to
characterize the BMFCs’ association.
The parallel combination of L1 and L2 involves two
BMFCs that have similar characteristics. The association
has quasi doubled Pmax (0.28 mW) in comparison with a
single BMFC (0.15 mW) (Figure 5-B & Table II). As
attempted, at the MPP, the cell voltages of the association
(VMPP) stay equivalent to the single BMFC’s one, near
300 mV (Table II). The internal resistance (Rint) of the

Figure 4. A) Theoretical dispersion of polarization curves in par-


allel associations. B) Polarization and power curves for identical
BMFCs in situ, L1 and L2 of the study. C) Power curves for iden-
tical BMFCs in situ, L1 and L2 of the study.

3.2.1. In parallel association


When electrical generators are connected in parallel, the
currents supplied by them are cumulative. Thus, current in-
tensity I recorded in the circuit is the sum of all currents
flowing through each cell. The power is then greater for a
given voltage. In addition, when a generator is down, the
others could still work (unlike the in series connection).
However, the disadvantage of this arrangement is that the Figure 5. A) Electrical chart of the in parallel association of
lowest generator voltage is imposed to all others. In our BMFCs L1, L2, L3 and L4. B) Power curves of in parallel BMFC
study, L1 and L2 are first connected in parallel, and their associations: □ to the L1–L2 association and ◊ to the L1–L2–L3–
association is characterized. Then, L3 and L4 are also con- L4 association, compared with the individuals BMFCs L1 (Δ), L3
nected in the circuit, in derivation with the first association. (x) and L4 (o).

548 Int. J. Energy Res. 2015; 39:543–556 © 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Microbial fuel cell P. Salvin et al.

associated BMFCs, got from the linear region slope of the 3.2.2. In series association
polarization curve, is 300 Ω. It almost corresponds to the Another way to increase the cell voltage could be to as-
value of the equivalent resistance of the two BMFCs in sociate BMFCs in series. In series-connected MFCs, the
parallel: individual voltages of each cell add up at the output while
a common current flows through fuel cells. The serial asso-
RL1;int RL2;int 700680 ciation is considered not only in terms of increased power
RL1-L2;int ¼ ¼ ¼ 340Ω production but also to increase voltage to an acceptable
RL1;int þ RL2;int 700 þ 680
level for real applications.
Nevertheless, the drawbacks of this type of association
By adding L3 and L4 in parallel to the previous associ- are:
ation (finally L1//L2//L3//L4), the maximal power point
(MPP) obtained is 0.55 mW for IMPP equal to 1.67 mA. i. Internal resistance generators are added to each
The theoretical association of these 4 BMFCs in parallel other and can reduce the current gradually as the
gives a maximal power of 0.62 mW for a current of number of cells increases;
1.79 mA (Table II). ii. If one generator is out of service, so is the entire
The maximum efficiency for this configuration at MPP circuit;
is defined in Equation 1 where POUT is the output power iii. The generator with the lowest intensity imposes it to
for the associated BMFCs and ΣPMPP is the sum of MPP all others. The power loss could be important
for each BMFC. It is about 88.7% at MPP. In this case, because some of the generators will not be used to
the BMFCs work at 99%, 98%, 87% and 91% of MPP, their maximum power point.
respectively.
The latter indicate that this association cannot provide
 the maximum potential power available.
η% ¼ POUT ∑ PMPP
100 (1)
In particular, in the case of BMFC, an application in situ
is not possible because the cathodes are in the same elec-
We note that reactors L1 and L2 operate at maximum trolyte, without separation [28]. So, in this study, only
efficiency which is not the case for both others reactors the laboratory BMFCs are considered for the in series asso-
L3 and L4. This is normal since the voltage imposed on ciation. The individual BMFCs L1 and L2 were stacked
all BMFCs is around 300 mV. That corresponds to VMPP after separating the two cells by transferring to another
(and thus Pmax) for L1 and L2 while this is not the case compartment the L1 BMFC system. Thus, the possible
for L3 and L4 (VMPP being around 385 mV). The last two ion exchange inter-cell was avoided. L1 was then placed
do not operate at MPP. The parallel association has alone in a 5-L bucket. There was a significant decrease in
allowed increasing the final power output (0.55 mW when its voltage value. Indeed, the cell voltage V1kΩ was
the best individual performance is 0.23 mW). 260 mV instead of 400 mV before the transfer. The transfer
With four equivalent BMFCs with the best performance and the volume change have resulted in the loss of perfor-
(L4), the maximal power output could be 0.92 mW, a value mance of L1. So for a better comprehension, L1 was then
close to 1 mW. So, several mW could be obtained if called L1*, and a new characterization was made by a po-
the surface area of the electrode was increased. In addition larization curve and power curve after the transfer in its
to this, this experiment is technically realizable in situ. new container.
However, the inconvenient is still the low cell voltage L1* and L2 cells have no similar characteristics (Table III).
which is not sufficient to supply the high majority of The performance of the in series combination will be limited
electronic materials. Researchers have conceived ‘power by the less efficient BMFC, L1*. VOC, the open circuit
management system’ and ‘voltage conditioner’ which are voltage, has increased significantly since it corresponds to
devices capable of amplifying the output cell voltage of the sum of the two elementary open circuit cell voltages,
BMFC [11,28,37]. approximately 1470 mV. The voltage increase is significant

Table III. Electrochemical characteristics corresponding to the maximal power Pmax of individual and series associated laboratory
BMFCs.

BMFC names L1*–L2 in series L1*–L2 in series L1*–L2 in series without L1*–L2 in series with
(individual or associated) L1* L2 (theoretical) (experiment) SC (simulation) SC (simulation)

Pmax in mW 0.07 0.16 0.23 0.20 0.196 0.226


Voc in mV 767 710 1477 1420 1445 1437
VMPP in mV 370 310 680 625 683 482
IMPP in mA 0.19 0.52 – 0.31 0.34 0.48
Rint in Ω 1620 680 2300 2120 2000 2000
Efficiency (%) – – 100 86 86 98.6
L1* is the L1 BMFC system after its replacement in an independent container.

Int. J. Energy Res. 2015; 39:543–556 © 2014 John Wiley & Sons, Ltd. 549
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P. Salvin et al. Microbial fuel cell

for power electrical applications. A combination of several 3.3.1. Modeling of BMFCs


equivalent BMFCs could achieve a voltage interesting to The theoretical maximum cell voltage of a BMFC is
recharge a micro-battery for example. never achieved, particularly with BMFCs because of volt-
The maximum efficiency for this configuration at MPP age drops and current drops. The output voltage is there-
is defined by (1) and equal to 86.5%. fore expressed as [49]:
As it was described in Figure 4, the non-uniform
manufacturing processes or microbial heterogeneity causes V ¼ V OC  ΔV ohm  ΔV act  ΔV trans (2)
dispersions between the BMFCs. Generally, during the ex-
periments, dispersions in the internal resistance were noted where VOC is the open circuit voltage.ΔVohm is the ohmic
(Tables II and III). The result is a non-optimized operation drop and it is the simplest to understand and to model.
of in series association since traversed by the same current, The voltage drop value is simply proportional to the cur-
BMFCs do not function at their MPP. rent, which is given by Ohm Equation 2

3.3. Simulation of operation with voltage ΔV ohm ¼ Rohm :I (3)


balancing circuit

The absence of bacterial activity in cells is one of the I is the current density given in A or mA.cm2, and Rohm is
reasons that cause the voltage reversal. The dispersions the ohmic resistance and should be given in Ω or kΩ.cm2.
between the associated BMFCs may also cause voltage re- ΔVact is the activation voltage drop and given by the so-
versal. Voltage reversal is detrimental to power generation called Tafel Equation 4:
because the concerned BMFC (the weakest) will absorb
the electrical energy of the others BMFCs. However, to ΔV act ¼ B:lnðI Þ (4)
optimize the efficiency, it is possible to use a voltage
balancing circuit with in series-connected BMFCs. The expression of the activation losses is valid when
Voltage balancing circuits are usually used for batteries I > 1A which is not a valid assumption in the case of
to expand their life [38,39]. Applications to supercapacitors MFCs. When currents below 1 A are considered, it can
and photovoltaic cells are made to improve the power gen-
eration [40,41]. Several methods are used to achieve the
voltage balancing for the batteries, and other methods are
used only to prevent the voltage reversal as performed with
solar cell.
The voltage balancing circuits designed for batteries
and photovoltaic cells are not adapted for BMFCs. The
main drawback of passive balancing circuits is that they
have a poor efficiency in the case of low-power generators
like BMFCs [42,43]. Methods that use inductors or trans-
formers to transfer energy have low efficiency due to
switching losses and magnetic losses [43,44]. Converter
architecture such as cûk [45], buck or/and boost [46],
full-bridge, flyback and quasi-resonant can be used for cell
balancing. Although these converters have an acceptable
efficiency, they are expensive and complex. The switched
capacitor and inductive shuttling methods are options
presenting theoretically higher efficiency. The switched
capacitor circuit (SCC) only requires switches (SW), ca-
pacitors (C) and a single oscillator [47,48]. In this method,
a capacitor is alternatively connected in parallel with the
BMFCs at FS frequency. When the BMFCs are unbal-
anced, the capacitor charges when it is connected to the
strongest BMFCs and discharges when it is connected to
the weakest BMFCs. The transfer of charges is limited by
the in series resistances of the voltage sources inside
BMFCs and the capacitor. These resistances include the
on-resistances RSW of the switches, the ohmic resistance
of the BMFCs and the resistance of the capacitors. These
are less area-consuming than inductive-based circuits and Figure 6. A) Features of analytical model and comparison with
countless in components. Therefore, the switched capacitor experimental polarization curve of L1*; B) features of analytical
circuits offer good perspectives for BMFCs. model and comparison with experimental polarization curve of L2.

550 Int. J. Energy Res. 2015; 39:543–556 © 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Microbial fuel cell P. Salvin et al.

be modified by an almost equivalent expression. The acti- L1* and L2 (0.767 V and 0.710 V, respectively, Table III).
vation voltage drop is modified as in (5): The slope of the polarization curve in the ohmic region allowed
determining the ohmic resistance (1620 Ω and 680 Ω, respec-
  tively, for L1* and L2, Table III). This was validated using
I
ΔV act ¼ B:ln þ1 (5) Prism software. The other parameters B, C, D, and E can be
C
determined using Prism software. The fitting method used is
nonlinear regression (least squares fit). The results obtained
where B and C are constants depending on the electrode
are presented in Figure 6. These figures show that the compar-
and cell conditions.
ison between analytical model (defined by Prism software) and
ΔVtrans is the mass transport or concentration voltage
the experimental polarization curve is very close to each other.
drop and given by Nernst equation ΔVtrans = D. exp(E. I),
In terms of electrical equivalent circuit, the above ana-
D and E are constants to be determined.
lytical equations can be represented by an ideal voltage
The equation for the operating voltage of a fuel cell at a
source and a number of electrical components connected
current density can be written as (6):
in series and responsible for the different voltage losses.
  A constant resistance represents the ohmic losses while
I the other losses are non-linear and are represented in
V ¼ V oc  Rohm :I  B:ln þ 1  D:expðE:I Þ (6)
C Figure 7 (model a) with variable resistances. This model
is valid in steady state because the experiences show
This equation defines the analytical expression of a po- non-immediate reaction of BMFC caused by the internal
larization curve with five parameters to be defined. A direct mechanisms (i.e. activation and concentration). The inter-
fitting of a polarization curve does not necessarily enable face between each electrode and its surrounding electrolyte
to identify all parameters precisely because different forms a capacitor. The combination of static and dynamic
parameters can govern similar effects on the polarization mechanisms can be represented in an electrical model:
curve. The ohmic resistance is therefore primarily deter- the effects of both concentration and activation overvolt-
mined using electrical impedance spectroscopy (EIS). The ages are modeled by a variable resistance connected in
other parameters are determined through fitting of the exper- parallel with a variable capacitor as in Figure 7 (model b).
imental polarization curve with the four-parameter equation It is simple to implement this model in MATLAB®: the
(Prism software). It is simple to model this equation using simulation results show that the capacitive effect of concen-
a spreadsheet (such as EXCEL), or programs such as tration is almost negligible compared to the activation.
MATLAB®. Voc was measured and it was determined for Therefore, the electrical model can be simplified as shown

Figure 7. Electrical equivalent circuits for a BMFC.

Int. J. Energy Res. 2015; 39:543–556 © 2014 John Wiley & Sons, Ltd. 551
DOI: 10.1002/er
P. Salvin et al. Microbial fuel cell

Figure 8. Results of simulation. A) Serial association of two MFCs represented by their electrical models. B) Polarization (solid line) and
power (dotted) curves Simulation (+, red) and experimental (o, blue). C) Cell voltage for each BMFC.

552 Int. J. Energy Res. 2015; 39:543–556 © 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Microbial fuel cell P. Salvin et al.

in the Figure 7 (model c). This model will be used to realize 3.3.3. Simulation of two BMFCs in series with SCC
simulation of BMFCs in series without balancing (and The application of SCC is represented in Figure 9-A. The
compared to experimental results) and with balancing global efficiency of the association is defined as Equation 1.
circuit (SC). The simulated efficiency of the association with changes in
switching frequency is plotted in Figure 9-B for RSW = 0.5 Ω
(low on resistance) and for various capacitors values C12. At
3.3.2. Simulation of two BMFCs in series without low switching frequency, the circuit is not useful and volt-
switched capacitor circuit (SCC) ages are not balanced. Efficiency for FS = 1 Hz is around
Figure 8-A presents the in series association of two 80% (66% for C12 = 500 μF). The efficiency increases with
BMFCs represented by their electrical models as defined switching frequency until 100 Hz, reaches up to 98% and
above. The V–I and P–I simulation curves for associated finally decreases for frequency beyond 100 Hz. The shape
BMFCs are given in Figure 8-B. The polarization and of the curve seems logical: indeed, efficiency decreases
power experimental curves are also shown in these figures. with increased frequency because it causes the increase of
We see that the simulated curves are very close to experi- the switching losses. The maximal efficiency (98.6%) is
mental curves, which validates the relevance of our electric reached for Fs = 100 Hz and a capacitor C12 = 100 μF.
model. At the maximum power point, the voltage of each Figure 9-C shows V–I and P–I curves for associated
BMFC is different, leading to a non optimal operating BMFCs with voltage balancing circuit for 10 KHz. When
point. For high values of current, the voltages V1 and V2 the BMFCs’ performances are widespread, the SCC
drift apart, eventually leading to a negative value of V1 as achieves good overall performances. Figure 9-D shows
represented Figure 8-C. This phenomenon is discussed as the cell voltage V1 and V2 for each BMFC. We note that
‘voltage reversal’. Voltage reversal is detrimental to power the voltage reversal phenomenon disappeared (compared
generation because the concerned BMFC (the weakest) to Figure 8-C for V1) thanks to the balancing circuit which
will absorb the energy instead of producing some. The allows increasing the global efficiency.
maximum efficiency for this configuration is of about The switched capacitor circuit is the most efficient volt-
86% at MPP for Rext = 2000 Ω (Table III). To increase age balancing circuit. It benefits from the fact that there is
the efficiency and avoid the voltage reversal, a voltage no switch in series with the BMFCs. The switches are only
balancing circuit was added to the in series association. crossed by the balancing current. A drawback is that it

Figure 9. A) Schematic switched capacitor circuit. B) Efficiency of the association vs the switching frequency Fs for various values of
capacitors. C) Polarization (solid line, +) and power (dotted, o) curves Simulation with SC. D) Cell voltage for each BMFC with SC.

Int. J. Energy Res. 2015; 39:543–556 © 2014 John Wiley & Sons, Ltd. 553
DOI: 10.1002/er
P. Salvin et al. Microbial fuel cell

requires a minimum of (n  1) capacitors with quite high Shewanella putrefaciens. Journal of Microbiology
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The study presented in this article has put forward several 7. Martins G, Peixoto L, Ribeiro DC, Parpot P, Brito AG,
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organic substrate. ation of the potential of various aquatic eco-systems in
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to be autonomous electricity harvesting systems, only fect of electrode assembly and water characteristics.
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of the French ANR through the Agri-Elec project (ANR- of a microbial fuel cell as a viable power supply:
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