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Journal of Power Sources 356 (2017) 438e447

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Journal of Power Sources


journal homepage: www.elsevier.com/locate/jpowsour

Energy sustainability of Microbial Fuel Cell (MFC): A case study


Tonia Tommasi a, b, *, Giorgia Lombardelli a
a
Department of Applied Science and Technology - DISAT, Politecnico di Torino, Corso Duca degli Abruzzi 24, Torino, Italy
b
Center for Sustainable Future Technologies, Istituto Italiano di Tecnologia, Torino Italy

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Energy sustainability analysis of


experimental results of lab-scale
MFC.
 Net energy balance results negative
due to energy expenditure to feed the
system.
 Other congurations have been taken
into account to reach positive energy
balance.
 The time to recover the initial energy
cost has been evaluated in all
congurations.
 Sedimentary FC and down-ow MFC
represent good perspective for
scaled-up system.

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

Article history: Energy sustainability analysis and durability of Microbial Fuel Cells (MFCs) as energy source are neces-
Received 15 January 2017 sary in order to move from the laboratory scale to full-scale application. This paper focus on these two
Received in revised form aspects by considering the energy performances of an original experimental test with MFC conducted for
22 March 2017
six months under an external load of 1000 U. Energy sustainability is quantied using Energy Payback
Accepted 25 March 2017
Available online 12 April 2017
Time, the time necessary to produce the energy already spent to construct the MFC device. The results of
experiment reveal that the energy sustainability of this specic MFC is never reached due to energy
expenditure (i.e. for pumping) and to the low amount of energy produced. Hence, different MFC ma-
Keywords:
Microbial Fuel Cells (MFCs)
terials and architectures were analysed to nd guidelines for future MFC development. Among these,
Energy sustainability analysis only sedimentary fuel cells (Benthic MFCs) seem sustainable from an energetic point of view, with a
Energy Payback Time (EPT) minimum duration of 2.7 years. An energy balance approach highlights the importance of energy
Sedimentary fuel cells (SMFC) calculation. However, this is very often not taken into account in literature. This study outlines promising
Wastewater treatment (WWT) methodology for the design of an alternative layout of energy sustainable MFC and wastewater man-
agement systems.
2017 Elsevier B.V. All rights reserved.

1. Introduction

Recently United Nations Conferences on Climate Change (COP


21 and COP 22) [1] have aimed to set out a framework for action to
* Corresponding author. Department of Applied Science and Technology - DISAT, limit dangerous anthropogenic interference with the climate and
Politecnico di Torino, Corso Duca degli Abruzzi 24, Torino, Italy. other environmental threats. The objective is to reach a global low
E-mail address: tonia.tommasi@polito.it (T. Tommasi).

http://dx.doi.org/10.1016/j.jpowsour.2017.03.122
0378-7753/ 2017 Elsevier B.V. All rights reserved.
T. Tommasi, G. Lombardelli / Journal of Power Sources 356 (2017) 438e447 439

carbon economy by 2050. For this reason, there is a high interest in power densities and hence decreased efciency [27]. Some ap-
biomass, sparked by the aim to valorise waste and biomass and to proaches have been evaluated in order to avoid energy loss when
encourage bio-economy [2]. Microbial Fuel Cell (MFC) is a relatively moving from small scale to large scale, to maintain the electrode
new technology that seeks to upgrade organic waste producing surface area to chamber volume ratio and to consider a stacking of
directly electric energy by using the electrons of the respiratory small-scale MFC assembled in a cascade [28]. On the other hand, for
chain. Microbes, present in the anode chamber, called anode WW treatment efciency, the high percentage of organics removal
respiring bacteria (ARB), oxidize fuel such as organic waste present guarantees mainly by aerobic treatments should also be guaranteed
in polluted wastewater (WW) before safely discharging it, gener- by MFCs in order to obtain satisfactory efuent standards. Zheng
ating electrons and protons. ARB carry out an oxidation (half-cell) and Zhen [29] installed an MFC system in a local WWT plant
reaction of organic matter, producing electrons and protons and feeding the primary efuent. This system consisted in 200 L
thus an electric current from biomass. Although conceptually modularized MFC consisting of 96 tubular MFC modules of 2 L
similar to batteries (both are constituted by an anode and a cath- hydraulically connected in a cascade of 8 MFCs through plug-ow
ode), fuel cells receive a continuous supply of fuel. For example, feeding and electrically connected in opportunely parallel and se-
hydrogen in the case of traditional Fuel Cells and organic material ries connections. The system exhibited effective treatment of pri-
in the case of MFC. mary efuent through the integration of bioelectrochemical and
Many congurations are under study, e.g. single or dual cham- aerobic treatment. Therefore, a solution could be to consider a rst
ber with [3] or without membrane (membrane less MFC) [4,5] and MFC step followed by a second aerobic one, such as activated sludge
sedimentary fuel cells, directly posed inside the natural environ- (AS) or trickling lter (TF) to guarantee the efciency required.
ments, such as seawater [6], lake [7,8], soils [9] or river [10]. Commercialization of MFCs therefore still to face some unsolved
Moreover, due to the interdisciplinary nature of this topic other issues. The problem of scale-up has been discussed in the preceding
research contributions regard the materials selection for MFC paragraph. A further issue is low energy density production, which
construction [11,12], design [5,13,14], biology [15,16], electronics is very often not taken into account in the research. In fact, it is
[17], electrochemistry and catalysts [18e21]. often substituted with only punctual power density calculations
Potential benets of MFCs from the technology point of view, that in many cases do not contextualize well the real behaviour of
concern not only energy benets (i.e. direct electrical energy gen- the system for long time operation. In this context the analysis of
eration or avoided energy if associated at decentralized wastewater MFC system using the energy sustainability criteria seem to be very
treatment plant) but also the operative stability of the process, due relevant even if the technology is in its infancy. The present study
to the self-regeneration of the microorganisms and their good investigates the energy balance of MFCs highlighting the higher
resistance to environmental stress. Ledezma et al. [22] were able to energy consumption of the system and offering attractive materials
develop a self-sustainable MFC stack in cascade with a total volume and conguration to increase the net energy production of MFC
of 0.8 L fed by articial WW capable not only of self-maintenance systems. Indeed, with every new technology it is important that its
(feeding, hydration, sensing and reporting) but also of producing environmental footprint is very clearly marked before it is applied
excess energy (maximum power output of the system ~1.3 W m3). on a large scale [30].
Removal of organic compounds from wastewater by anodic This work starts from the energy analysis of two-chamber MFC
oxidation has been proposed by many researchers as energy ef- with graphite electrodes continuously fed by synthetic wastewater
cient treatment technology [23]. On the one hand, no energy is operated for six months under an external load of 1000 U. The
consumed for conventional aeration (1 kWh kg1 COD) and on the energy analysis was pursued by the evaluation of the net energy
other hand energy can be recovered from the substrate. The theo- production and the evaluation of the Energy Payback Time (EPT)
retical maximal value that could be recovered is 3.8 kWh kg COD1. parameter. The analysis was conducted considering the obtained
Currently, wastewater treatment systems are mostly based on the power of the experimental device and the energy production dur-
well-established activated sludge process. Although using activated ing the test time. After the energy analysis of the experimental
sludge produces superior results, the process is energy-intensive device and the identication of the larger energy costs, several
and requires high capital and operation maintenance costs [24]. hypotheses are advanced in order to visualise possible congura-
In fact, activated sludge needs aeration, which can count up to 75% tions of MFC and alternative materials to meet the energy sus-
of wastewater treatment plant (WWT) energy costs, while the tainability. The results highlight the importance of conducting a
treatment and disposal of sludge may count up to 60% of the total careful analysis to link research and industry, in order to develop a
operation cost. Wastewater treatment requires about 0.5e2 kWh performant and sustainable process for real-scale applications. This
m3 depending on the process and WW quality [25,26]; interest- process should take into account the energy it generates and
ingly, it contains 3e10 times the energy needed to treat it [25]. By spends as well as the stability and durability of the system.
extracting this hidden chemical energy, WWT can be turned into an
energy-yielding process, or at least it can reduce operation energy 2. Experimental
costs, depending on the energy obtained from the MFC system and
WW plant design. The MFC system is of great interest because of its 2.1. MFC design and materials
dual role as both wastewater treatment device and energy gener-
ation device. However, there are some open questions to be The MFC device consists of two circular chambers, the anode
considered regarding the technical viability of MFC technology for and the cathode; both compartments are made of Poly-
congurations scaled-up to real-world operational dimensions methylmethacrilate (PMMA), wide 12 cm in diameter and 1.5 cm in
[25]. MFC very often work in sub-liter dimensions and without depth, and separated by a cation exchange membrane (CEM) (CMI
economical optimization of materials. Transferring laboratory-scale 7000, Membranes International Inc.) as shown in Fig. 1. The total
devices and knowledge, to systems that must compete economi- volume of each empty chamber is around 170 mL (Fig. 1). Experi-
cally with existing industrial systems, is a huge challenge. There- ments are conducted using two identical MFCs operated under the
fore, an important preliminary step in the design processes is to same conditions in order to estimate the uncertainty of the system.
establish the expected performance of the system. In addition to The experiments are performed using commercial graphite felt
the structural material of an MFC, a limitation appears regarding both as anode and cathode electrodes (Soft felt SIGRATHERM GFA5,
the size of MFCs, whereby large-volume units tend to have lower SGL Carbon, Germany); the conductive materials are mechanically
440 T. Tommasi, G. Lombardelli / Journal of Power Sources 356 (2017) 438e447

Fig. 1. MFC congurations and materials involved in the experiment.

connected with a graphite rod of 5 mm in diameter to ensure an is recommended to facilitate charge movements (electrons toward
effective electrical current conductivity. The two MFCs operate in a electrodes and cations towards CEM membrane), gaseous product
continuous mode using as external charge of 1000 U resistor for stripping and homogeneous diffusion of reagents. Anyway, in the
each one; the test is carried on for more than six months at room following calculations, the energy for mixing through recirculation
temperature of 24 5  C. Fresh sea water (Arma di Taggia, Italy) by high-speed ux has not been considered, because with the same
sample is used as source of active microbial consortia. Seawater has experimental apparatus, similar results carried out with and
been taken as source of bacteria thanks to their diversity and without recirculation have been obtained.
importance into the biogeochemical cycles and transformation of To calculate the energy produced by MFCs, the cell voltage (DV)
nutrients [31]. for both cells is continuously measured every 60 s using a data
The sea water has been previously enriched as described in logger (Agilent, 34972A, The Netherlands) with an external resistor
Ref. [32]. The anolyte consistes of anode buffer solution composed (R) of 1000 U. The current (I) is calculated from DV and R using
of 30% v/v of fresh sea water and 70% v/v of inorganic salts buffer Ohm's law: I V$R1, and consequently, the power is obtained
(i.e. Na2HPO4$2H2O (8.2 g L1) and NaH2PO4$H2O (5.2 g L1)), (P DV I). Thus, the energy produced (EMFC) by MFC in joule (J)
supplemented with inoculum (50 mL), sodium acetate (1 g L1) and during six months of continuous operation is calculated as the
peptone (1.25 g L1). The total anolyte volume (500 mL) is integration of the electrical power in the time (t) by the following
continuously recirculated by a peristaltic pump (ISMATEC - Equation (1):
ISM404B, Germany) from the anode vessel through the anode
compartment at a ow rate of 1 L h1. Before starting the tests, N2 is Zt
owed to ensure anaerobic conditions in the anode chamber. A EMFC I$DV$dt (1)
concentrate synthetic anode inuent is continuously fed by a multi- t0
channel programmable syringe pump (NE-1600, USA) at a ow rate
of 0.42 mL h1 in order to provide to the individual anode solution For the energy balance calculation, a month mean average value
of MFCs 1 g L1 sodium acetate and 1.25 g L1 peptone per day. The of the recovered energy (EMFC) between the two MFCs has been
catholyte consistes of potassium ferricyanide (500 mL at 6.58 g L1) taken into account.
aqueous solution in a buffer solution of inorganic salts of the same The net energy produced (Enet) in an MFC is the difference be-
concentration as that of anode, which is continuously recirculated tween the energy produced under form of generated electricity
by a peristaltic pump from the cathode vessel through the cathode when circuit is closed (EMFC), and the energy spent to feed the
compartment at a ow rate of 1 L h1. The cathode solution is system with the pump (namely the direct energy, Edirect). The last
refreshed whenever the solution begins to bleach out, indicating term involves all the direct energy terms of different nature (elec-
the consumption of catholyte by reduction reactions. Fig. 1 shows trical and thermal if present) occurring in the system; furthermore,
the experimental apparatus and the materials involved into the if organic waste is used and some pre-treatments processes are
experimental set-up and taken into account for the energy analysis. employed, it is necessary to consider these energy terms too. In the
present study, only the energy for feed pumping is considered due
to the absence of other energy terms.
2.2. Energy balance
Therefore, the net energy is evaluated with the following
equation:
In order to perform the energy sustainability analysis of the
process, the methodology reported in Di Addario et al. [33] is
Enet EMFC  Edirect (2)
exploited. The rst step to perform the energy analysis of the sys-
tem is the evaluation of the net energy produced, i.e. the energy where EMFC is calculated by Equation (1) and Edirect by Equation (3),
produced by the device minus the direct energy spent to run the which depends on the pump power supply and the utilization time
system itself. In the present study, in order to perform the energy of it during the course of the experiment (syringe pump for the
balance, both energy recovery by the MFCs (EMFC) and direct energy feeding):
expenditures (Edirect) have been taken into account. Some MFCs, as
that one described in the present study, need continuous feeding of Edirect Ppump  Dt (3)
substrates, guaranteed by the pumping system. Moreover, agitation
T. Tommasi, G. Lombardelli / Journal of Power Sources 356 (2017) 438e447 441

The energy calculation, which takes into account produced and at the early stage: this fact does not permit the evaluation of all the
consumed energy, is referred to 28 days for month, due to half a day other indirect energy terms needed to run a plant [23]. tm is the
maintenance every week for tubing cleanup and some other time necessary to recover the energy required to balance the spent
maintenance. The above procedure has been applied for the energy energy to produce the materials for MFC construction: only after
evaluation of other literature works, in which only the power this time the MFC really produces a useful energy to feed the so-
densities are reported, in order to consider the same direct energy ciety. tm is calculated as shown in the following equation, where
of our experimental device. Ematerials is the energy spent to produce material and Pw, used
instead of yearly net energy produced (Equation (5)), is the power
of the MFC obtained:
2.3. Energy sustainability analysis
Ematerials Ematerials
Even if a technology has a positive net energy value, it is not tm year (6)
Enet =td Pw
necessarily sustainable, since another important aspect must be
contemplated, that is the spent energy to produce the system, i.e. The MFC system used to perform the experiment is constituted
the expenditures to produce materials and chemicals used to run by two-chamber MFC in PMMA, various plastic connections,
the system. Then, if the net energy of the process is positive, it is stainless steel screws and bolts (Fig. 1). In the process, materials
necessary to move to the second step of energy sustainability produced elsewhere are usually used.
analysis, which consists in the evaluation of the energy spent to
produce the materials for the construction of the MFC. Hence, it is
possible to evaluate the Energy Payback Time (EPT), which is, given 3. Results
the actual power, the time necessary for the system to produce an
amount of energy equal to the already spent one. Consequently, EPT 3.1. Experimental case
represents the minimum duration time of the MFC. The energy
embedded in the material is called Indirect Energy, which is Over the six months of the duration of the test, the two MFCs,
required for the evaluation of the EPT. The indirect energy con- demonstrates a similar trend in voltage output, i.e. 0.65 V 0.07 V,
nected to material is calculated using the Global Energy Require- under 1000 Ohm resistances. The observed uctuations depend
ment (GER), which allows to convert all the material ows into mainly on from night and day temperature variations and on some
energy units and to evaluate the energy content in each kilogram of feeding stops due to obstruction of silicon tube or connector. The
material, through equation (4): voltage values over the second month of testing are more stable,
  probably due to better bacterial adhesion. On the other hand, the
X MJeq Open Circuit Voltage (OCV) values measured during half a day of
Ematerials GER  mmaterial kg (4)
kg maintenance is 0.78 0.4 V. The power obtained from each cell is
0.40 0.08 mW (power density respect to surface anode chamber
The GER of each material is evaluated by utilizing the SimaPro
~35 7 mW m2). On average, the monthly energy produced by our
7.2.4 software and the Ecoinvent database 2.0, Ematerials are evalu-
MFCs after start-up is 1000 200 J for month (~279 48 Wh). This
ated by considering GER and the quantity of the material present in
value is obtained as mean value of the two devices considering the
the experimental device. The chemicals for synthetic wastewater
total energy produced in the six months of the operation.
and catholyte are disregarded in the energy analysis, since the nal
The power supply of the syringe pump is of 2.8 W, which cor-
aim is to use organic waste or water from natural environment as
responds to 6.8 MJ month1. Thus, for the experimental MFC tested,
fuel for the reactions occurring at anode (oxidation) and cathode
the net energy balance is negative (Fig. 2). It is therefore evident
(reduction).
that the process considered is not energetically sustainable. For this
The EPT takes into account all the energy terms (including in-
reason, the calculation of tm does not make sense.
direct energy) and in mathematical terms is as follows:
The amount of energy that can be obtained anywhere by MFCs is
Eindirect relatively low (ranging between 0.001 and 10000 mW m2) [11],
EPT year (5) and the optimistic predicted power density is close to 17 W m2
Enet =td
[34]. This value has been taken as reference (Hypothetical MFC) for
In this study, in the term Eindirect (that includes all the contri- the energy calculation presented in this work, and represents the
butions of a process, which involve energy expenditure in an in- highest obtainable power. With ~35 mW m2 (~2 W m3) case the
direct way) only Ematerials is considered as the MFC technology is still present experimental case is positioned around the middle of the

Fig. 2. Energy balance analysis on MFCs fed by syringe pump in two cases: current experimental MFC and the obtainable power (Hypothetical MFC).
442 T. Tommasi, G. Lombardelli / Journal of Power Sources 356 (2017) 438e447

Table 1 source.
Weight of materials taken into account in the energy analysis of down-ow system As mentioned previously, indirect energy value is calculated
and GER value of its.
considering materials used for the construction of MFC congura-
Material Weight [g] GER [MJeq$kg1] tion described in Fig. 1 and Materials and Methods through the
Graphite felt (anode) 1.8 0.53 quantication of the GER value for different materials (reported in
Graphite felt (cathode) 1.8 0.53 Table 1).
Synthetic rubber stoppers 13.0 91.81
Stainless steel screws and bolts 130.0 53.40
Silicon tube 45.0 62.65 3.2. Hypothesis of down-ow system
Pysh-t polypropylene connectors 19.5 79.26
Polypropylene syringes 10.0 75.11
Polypropylene cable glands 3.8 (*4) 121.59 Using a gravitational fall of water inside the MFC system can
Polymethylmethacrylate 1100.0 150.21 help minimise the energy expenditure. In fact, using a down-ow
Graphite rods 8.0 (*2) 0.53 system, organic water is fed from above to the fuel cell, and is
Glass bottles 350.0 41.70 pulled down by gravity thus rendering mixing and pumping un-
Cation Exchange Membrane 7.0 34.82
necessary, with a positive outcome on the overall energy efciency
of the device (Fig. 3). In this case the direct energy expenditure is
equal to zero, and the net energy is equal to the energy produced,
range. This power density, which is relatively low with respect to which is positive. Therefore, the process is sustainable in this rst
recent studies, seems to be mainly due to the relatively big design step and it is important to assess the indirect energy and conse-
(113 cm2, 170 mL per chamber), but also to standard materials quently to calculate tm.
without catalysts or treatment of electrode materials. For example, Fig. 4 shows a ow chart that represents global energy request
Fraiwan et al. [35] obtained 49 W m2 with a synthetic substrate, to construct the experimental MFC, clearly showing the contribu-
primary clarier inuent and a very small surface anode of only tion made by various materials constituting the cell. Overall, the
0.28 cm2. Moreover, the resistance of 1000 Ohm applied value calculated for Ematerials is equal to 195 MJeq. As can be
throughout the experiment presented here was chosen because it is observed, PMMA is the material with the highest cost of energy
in the middle of the resistance range and is well supported for MFC (84.6% of total Ematerials), i.e. 165 MJeq from a total of 195 MJeq.
tests. Nevertheless, this resistance does not correspond to the In the hypothesis of positive net energy balance down-ow
optimal resistance, that makes it possible to work near Maximum system (obtained without the use of pumps) the tm value, which
Power Point Tracking (MPPT). A polarization curves conducted in represents the time necessary to recover energy expenditures for
the middle of the experiment (data not provided) shows an MPPT the MFC investment, is equal to 16,250 years. This high value,
at ~ 680 Ohm, where the power obtained is greater than 22%. mainly due to the very low power output and the high energy re-
Even with the hypothesis of a power density of 17 W m2 (Fig. 2, quirements for material synthesis (Ematerials), clearly indicates that
Hypothetical MFC), the energy balance is barely negative the system is not sustainable from an energy point of view.
(23 J month1). Note that the energy obtained by experimental Therefore, it is impossible to attain the energy sustainability for this
MFC is 0.012 MJ y1 (against 5.58 MJ y1 for hypothetical MFC): for conguration and it would be unfeasible to extract energy for such
this reason, it is difcult to see that value in Fig. 2. The experiment is a long period of time. Nevertheless, this analysis highlights the
conducted with standard graphite materials and congurations, importance of material selection for energy sustainability, in real
using mixed culture as inoculum, for this reason probably the applications. As can be observed in Fig. 4, PMMA is the material
performances are low. with the highest cost of energy with a GER equal to 150.21 MJeq
Therefore, the conguration of MFC constituted by two- kg1. In addition, more than 99% of the total energy is coming from
chamber device and pumps is not suitable as source of energy. non-renewable energy sources (both fossil and nuclear, 93.9% and
Moreover, when scaling up, a number of further energy costs may 5.4%, respectively). However, the substitution of PMMA with other
also need taking account of specically, pretreatment of biowaste in materials, i.e. PVC permits to cut down the energy costs into half,
order to facilitate digestibility of the waste, mixing, and in some responding not only to the energy sustainability issue but also the
environmental conditions, heating the feed. These costs may economic one. For example, as shown in Table 2 the energy costs
further reduce the advantages of MFC technology as an energy linked to alternative and conventional materials as stainless steel,

Fig. 3. Energy balance analysis of down-ow system, for both Hypothetical and Experimental MFC. Note: the energy obtained by experimental MFC is 0.012 MJ y1, for this reason it
is difcult to note its contribution on the graph.
T. Tommasi, G. Lombardelli / Journal of Power Sources 356 (2017) 438e447 443

Fig. 4. Flowsheet of the global energy demand for the construction of experimental MFC; contributions lesser than 1% are not considered.

PVC and concrete production are minor compared to PMMA. sustainability of the process is improved since there is a lower value
According to the GER values reported in Table 2 and considering of Eindirect in both cases. Consequently, tm for the two alternatives is
the amount of these materials and the presence of other materials still very high: 7375 years, 8000 years and 2732 years for steel, PVC
in the MFC, Ematerials value of 88.5 MJeq, 96 MJeq and 32.8 MJeq are and concrete, respectively; and again, not in line with the energy
obtained if the MFC structure is made by stainless steel, PVC and sustainability criteria. However, a positive note to underline is that
concrete, respectively. electrode materials (both felts and rods), which are the key-point of
It can be observed from Table 2 that the greater energy impact the MFC devices, require a very small percentage of energy, with
still derives from the structure of the MFC, but overall the respect to the other materials synthesis, as shown in Table 1.
Indeed, the energy linked to CEM membrane and graphite which
constitutes anode and cathode are both less than 1% of the total
Table 2 energy requirement. In particular, 0.12% and 0.001% for CEM
Energy impact for Polymethylmethacrylate (PMMA) and alternative materials such
membrane and electrodes, respectively.
as Stainless steel, Polyvinylchloride (PVC) and Concrete.
As an example, stainless steel has been evaluated as an alter-
Impact category [MJeq kg1] PMMA Stainless steel PVC Concrete native material for MFC construction, due to its extensive use in
Non-renewable, fossil 141 45.4 40 0.612 chemical and biological reactors. However, considering that high
Non-renewable, nuclear 8.03 3.47 19.3 0.152 corrosion resistance is a necessary condition for fuel cells including
Non-renewable, biomass 0 0 4.21E-08 0
MFCs since operating environment could be extremely corrosive,
Renewable, biomass 0.218 0 0.00134 0.036
Renewable, wind, solar, 0.113 0 3.63E-05 0.00132 its use is discouraged, for less than a protective layer of high
geothermal corrosion resistance materials, such as polymers. Consequently, in
Renewable, water 0.851 4.43 0.984 0.0372 the following paragraphs, stainless steel will not be considered as
Total GER 150.21 53.4 60.29 0.8385 an alternative material for MFC manufacturing. On the other hand,
444 T. Tommasi, G. Lombardelli / Journal of Power Sources 356 (2017) 438e447

Fig. 5. Energy balance analysis of MFC inserted into WWT plant (a), for both Hypothetical and Experimental MFC. Fig. 5b refers to experimental apparatus (with pumping energy
expenditure), and Fig. 5c regards the hypothesis of a down-ow system (without energy expenditure).

the use of concrete, has the advantages of low energy and cost The calculation has been performed considering the ow-rate of
requirements but it is less appropriated for MFC development. the system under study, and hence water treated each month. In
order to calculate energy avoided, the cost of 0.5 kWh m3
(equivalent to 18 MJ m3) has been taken as a reference, consid-
3.3. Hypothesis of wastewater treatment
ering a mean value according to different conditions both
geographical and building choices. The avoided energy in the
MFCs are mostly studied for a combination of two advantages,
proposed MFC is 0.004 MJ month1 treating 0.2 L month1.
wastewater treatment and electrical current production, in a sus-
Results shown in Fig. 5 reveal that the net energy balance of MFC
tainable way [36,37].
integration on biological treatment lines with experimental MFC, is
Wastewater treatment consists of a combination of physical,
still negative (- 81 MJ year1) in the case of pumping system
chemical and biological processes and operations to remove solids,
present (direct energy expenditure to be considered in the bal-
organic matter and sometimes nutrients from wastewater: it in-
ance), instead in the case of down-ow system it is positive
cludes several steps, from preliminary (low degrees of treatment)
(0.06 MJ year1), i.e. with zero direct energy spending; the energy
to secondary, tertiary and/or advanced wastewater treatment [38].
request to treat the water is of the same order of magnitude of the
Generally, secondary treatment follows primary treatment (mainly
energy produced by MFC (1000 J month1). For a hypothetical MFC
consisting of mechanical removal of materials) and involves the
with 17 W m2 of power, net energy balance leads to the same
removal of dissolved biodegradable materials and colloidal organic
conclusion as of the experimental power. In the case of down-ow
matter using aerobic biological treatment processes. The prospect
system, the net energy is positive and hence, it is possible to
of using MFC between primary and secondary treatment would
calculate tm. It is greater than 500 years for all materials taken into
help achieving the fascinating concept of neutral-energy operation,
account (i.e. PMMA, steel, PVC and concrete). The minimum tm
stable treatment performances, less resource consumption and a
value of 546 years is for concrete. Hertle et al. [36] performed an
low environmental footprint [39].
LCA to compare the environmental impact of using MFC for WWT
The output of MFC used in the rst biological treatment of WWT
and found that the negative environmental impacts are mainly
process is not only the energy production but also the function of
associated with electricity consumption in the various process units
WW purication, which in energy terms is translated as energy
and transportation/disposal of biowaste; on the other hand, envi-
avoided, considering that the substitution of aerobic treatment
ronmental benets depend on the displacement of fossil fuel based
with MFC unit permits to avoid the energy expenditures associated
electricity generation with electricity generated by MFC technology
with the aerobic step of WWT. According to the degree of treatment
in WWT process. Also in this study, the main drawbacks are the
required, a further biological step could be integrated. This further
resource and emissions intensive materials required for MFC con-
step of aerobic treatment, coupled with the partial treatment by
struction. These results are hence in line with the present study
MFC system, offers a number of advantages: lower hydraulic
where both studies highlight the relevance of materials selection
retention time, lower oxygen demand (and hence lower pumping
and their development.
expenditure) and a smaller reactor. This concept is the same as the
one used in the Life Cycle Assessment of system that added value to
waste, avoiding its disposal for instance in landll with associated 3.4. Hypothesis of sedimentary fuel cells
negative energy and environmental impacts.
The energy avoided term (Eavoided) represents credits for the In order to consider situations where the construction materials
proposed system and not debts. In the present conguration, this are not required, MFCs could be directly posed in natural envi-
means that the energy avoided associated to WWT of this system is ronments which are naturally rich in organic matter (e.g. lakes,
not represented in terms of energy spent but in the balance this seawater, soils) with light structure and without pumping system,
value will be added up to the energy produced (eq. (7)): necessary for feeding and mixing (Fig. 6b). In this case, the net
energy balance results positive (direct spend energy is equal to
Enet EMFC  Edirect Eavoided (7)
zero). Moreover, the necessary material to build sedimentary fuel
Nonetheless, the tm calculation remains the same. cell (Benthic MFCs -SMFCs) requires a lower energy contribution
T. Tommasi, G. Lombardelli / Journal of Power Sources 356 (2017) 438e447 445

Fig. 6. Materials and GER for Sedimentary Fuel Cells conguration (a,b) and ow sheet of materials involved (c).

(Fig. 6c). In fact, it is constituted by an anode embedded into the constituted by a capacitor to store energy, a voltage comparator to
sediments where oxidative reactions occur in absence or limitation trigger the system for repowering and a change pump/DC-DC
of oxygen and a cathode, oating at water-surface, where reductive converter to boost the potential, avoiding completely the use of
reactions of oxygen or other compounds occur. Anode and cathode battery. With this system they solved two major challenges related
are connected by titanium and plastic-covered copper wire to powering wireless sensors: the increasing of the low potential
together with an external load between them. With this congu- (from ~0.3 V to 3.3 V) and the repowering of the system when there
ration, MFC could run as energy harvesting system, permitting the was not enough power to operate. The optimized electronics in-
powering of sensors and electronics in remote terrestrial area (i.e. tegrated with MFCs demonstrate to be an efcient way to manage
environmental monitoring). The use of copper wire requires plastic at the best the low energy density produced. Continuous power
insulation, in order to isolate it from the environment, permitting harvesting from renewable and locally available sources is a strat-
the creation of a potential difference between the anaerobic anode egy to either replace batteries or to recharge them over time. These
and the aerobic cathode. Moreover, titanium wire is often necessary energy supply systems should be reliable and they should not
to guarantee watertight seal between carbon materials and the require human intervention over relatively long periods, permit-
copper wire, in both anode and cathode terminal. Fig. 6a reports the ting to power sensors in remote area as reported in Ref. [41], where
quantity taken into account, considering for electrodes the same a meteorological buoy (ca. 18 mW average consumption) measuring
quantity as of experimental case. Copper wire of length 20 m and air temperature, pressure, relative humidity and water temperature
titanium wire of length 0.4 m is supposed in this case. was powered by SMFC. Optimized conguration of SMFCs, reported
Energy sustainability analysis for this conguration gives a tm of by Ref. [42] arrive up to 2.5 W m2 for scaled-up conguration with
2.7 years using anode and cathode in graphite and 20 m of copper multiple anodes/electron collectors in real ocean water and sedi-
wire and avoiding the use of titanium wire (with a total value of ments. Instead, in the case of oating MFC [8] where the distance
Ematerials equal to 0.033 MJeq year1). In other words, this means that between anode and cathode is not so long as in the case of ocean
if the system works more than 2.7 years, the initial energy invest- SMFC, power values smaller than Ref. [38] could be obtained.
ment is recovered and from there on produces useful energy.
However, the use of titanium wire, even with a length of only 0.4 m,
increases the tm to 42.5 years. In fact, the value of the GER associ- 4. Discussion
ated with titanium wire is equal to 4.9 MJeq$kg1, a much higher
value than that of copper wire, equal to 0.015 MJeq$kg1. The results presented in this paper point-out that MFC working
The Sedimentary Fuel Cells (Fig. 5b) like other MFC congura- time necessary to meet sustainability criteria depends on the
tions, could be integrated with other renewable energy sources (i.e. conguration and materials used. Experimental set-ups require a
wind and photovoltaics) in order to permit a stable although low- considerable number of years to recover the energy investment.
density energy level, as opposed to solar and wind energies. This makes them, considering human-life, unsustainable even if
Nevertheless, most sensors or electronics cannot operate with only MFCs possess a unique feature in the eld of fuel cells, i.e. they can
the low MFC potential output. Considering this, Donovan et al. [40] directly harvest chemical energy from several classes of wastes,
developed a power management system (PMS) to power inter- and/or recover it from several not puried organic substrates
mittently wireless temperature sensor using SMFC. The PMS was naturally present in different environments. The use of pumping
systems, for feeding and mixing is energetically impacting on the
446 T. Tommasi, G. Lombardelli / Journal of Power Sources 356 (2017) 438e447

Table 3
A brief account of the tm results obtained from solutions taking into account in the present study.

MFC-Case study tm [years] tm [years]b tm [years] tm [years]b


(experimental power) (experimental power) (theoretical power) (theoretical power)

Experimental /a /a /a /a
Down-Flow PMMA 16250 3250 34.95 34.66
Down-Flow PVC 8000 1600 17.2 17.06
Down-Flow Concrete 2732 546 5.87 5.82
Sedimentary (only copper wire) 2.7 0.006
Sedimentary (titanium wire addition) 42.5 0.09
a
The net energy is negative.
b
considering the energy avoided linked to WWT (Sedimentary fuel cell was not used for WWT).

net energy balance, to the extent that the energy produced by MFC (17 W m2) has been considered for the tm calculation. This means
is negligible compared to the high energy demand by the pump. that to overcome the critical issue of time necessary to recover the
This effect could be minimized in a down-scaled system, where energy spent for the construction of MFC system, research should
pumps are absent. Down-ow systems make it possible to avoid the be focused on biological design and materials to increase power
pumping system and to obtain a positive net energy balance. production in long-term experiments. The selection and growth of
However, although low-energy consuming materials are used, such most electroactive microorganisms seems to be one of the most
as PVC or concrete, energy sustainability is not reached. The system important factors contributing towards the energy sustainability.
proposed has a typical laboratory conguration that should be Indeed, by the evaluation of energy payback time using the
opportunely adapted for scaling-up manufacturing. Some critical maximal value of power density of 17 W m2, it decreases in all the
bottlenecks of lab-experimental design can be overcome with situations analysed (Table 3). In particular, for the sedimentary MFC
bigger reactors technologically with a cost-effective design. For from 2.7 years it decreases to 0.006 year. Considering a more ef-
example, the EPT calculation for anaerobic digestion technology for cient (Ehypothetical) system compared to the experimental MFC, the
the production of H2 and biogas in two reactors in steel varies with values sharply dropped for down ow congurations, reaching
diameter. For diameter 4 m the EPT is about 9.8 years and it values of 35, 17 and 6 years for PMMA, PVC and concrete, respec-
decreases slowly (EPT 6.7 year for 10 year). Instead for diameter tively. Another relevant aspect on sustainability issues is reducing
<4 m EPT grows exponentially to ~40 years for reactor of 0.5 m of the production of materials: for example, the raw materials used to
diameter [43]. Thus, the choice of suitable materials and the manufacture methyl methacrylate (MMA) or PVC could be recycled
consideration of energy impact on the sustainability of a technol- and reused in the same technology or extruded into new products.
ogy are key for planning emerging energy technologies. Using recycled material, not only reduces the use of raw materials,
Energy sustainability is reached in 2.7 years only in the case of but also reduces waste, thus, saving energy.
sedimentary fuel cells, where many materials (such as frameworks
and connectors) are avoided and the system is completely 5. Conclusions
immersed in the natural environment. In the case of considering
the immersion of MFC in the oxidation basin of a wastewater The paper aimed to perform a case study on the energy sus-
treatment plant, the energy obtained partially helps to reduce the tainability of a lab-scale MFC, considering the experimental
energy cost of aeration. obtainable power and a theoretical one. Unfortunately, the energy
According to the author's knowledge, there have been not sustainability is not reached under any circumstances. Neverthe-
studies presented in literature considering the energy sustainabil- less, in the present paper some suggestions for the future trends of
ity of MFCs and taking into account the net energy produced and research in the eld of MFC are given. First of all, possible energy
the tm. For a practical application, the MFC process should also be sustainability could be reached by the use of sedimentary MFC,
robust and stable without extra investment of energy for mainte- which helps to avoid energy expenditure necessary to produce
nance in a long-term run [39]. For instance, particular materials or container of the system introducing the electrodes directly in the
treatment that increase power density, should be critically environment. Furthermore, the removal of organic matter if MFC is
considered for the mechanical and biofouling resistance in the long incorporated into WWT saves energy for the complete chain of
period, or their capacity to maintain unaltered characteristics in the treatment, thus, decreasing the aeration costs and sludge produc-
time and for scaled-up system. In our previously study, MFC shows tion. Moreover, a more efcient system producing more energy
very higher performances thanks to PANI deposition on carbon felt compared to the experimental study, can drastically reduce the
[44] compared to pristine carbon felt, but after 4 months of the energy payback time. Lastly, attention needs to be focused on the
experiments with continuous feeding [45], the PANI deposition has selection and use of material synthesis and architecture of MFC
been lost in the medium causing a dramatic drop of power per- system, in order to reduce energy expenditures for their con-
formance and hence, the energy generation became comparable struction and the direct energy necessary for feeding and mixing
with standard carbon felt, or even worse. Materials and their the system by pumps.
treatments, though have a key-role on the device performance, for
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