Microbial Fuel Cell

Fundamentals
Ref:
B. E. Logan, et.al. “Microbial Fuel Cells:  Methodology and
Technology"Environ. Sci. Technol., 2006, 40 (17), pp 5181–5192

1
 and equipment, indica
for a paper that provid
MEDRED: reduced mediator
this information. In this
MEDOX: oxidized mediator types of MFCs, provide i
and give examples of m
not be considered an en
and describe methods o
to provide information
cating or advancing M
mation is available o
(www.microbialfuelcell

MFC Designs
Many different configur
2 and 3). A widely use
chamber MFC built in
usually of two bottles
separator which is usu
(CEM) such as Nafion (1
salt bridge (27) (Figure
choose a membrane tha
FIGURE 1. Operating principles of a MFC (not to scale). A bacterium chambers (the CEM

Microbial Fuel Cell

in the anode compartment transfers electrons obtained from an
electron donor (glucose) to the anode electrode. This occurs either
through direct contact, nanowires, or mobile electron shuttles (small
spheres represent the final membrane associated shuttle). During
membrane, PEM), but o
acceptor in the cathode
H-configuration, the m
the tubes connecting t
If you imaging electron production
fuel cell protons are
as a battery alsotransforms
that produced in excess.
chemical Theseenergy into
protons migrate through the cation exchange membrane (CEM) into tube itself is not neede
electricity, then microbial fuel cell is a device that use microorganisms to
kept separated, they ca
the cathode chamber. The electrons flow from the anode through
generate electricity instead
an external of catalysts
resistance in chemical
(or load) to the cathode wherefuel cell.
they react the membrane and clam
with the final electron acceptor2 (oxygen) and protons (26). (Figure 2b). An inexpen
a glass tube that is hea
 Anode
• The bacteria live in the anode and
convert substrate to carbon dioxide,
water, and energy.
• other oxidation reactions produce
products other than CO2 can also
happen, for example, fermentation of
glucose into alcohol
• Various substrates like glucose and
acetate can be used.
• most sugars and volatile fatty acids
are potentially food for bacteria
• The bacteria are kept in an oxygen-less
environment to promote the flow of
electrons through the anode.
• if there is abundant oxygen in anode,
electron will be consumed by oxygen
FIGURE 1. Operating principles of a MFC (not to scale). A bacte
in the anode compartment transfers electrons obtained fro
3
electron donor (glucose) to the anode electrode. This occurs e
through direct contact, nanowires, or mobile electron shuttles (
 Electric Circuit
• After leaving the anode, the
electrons travel through the
circuit. Rext
• These electrons power the
load.
• The voltage multiplied by the
current shows the power.
• I = V/Rext
• P=V2/Rext

4
Proton Exchange Membrane
and equi
• Proton exchange membrane (PEM) for a pap
only permits H+ to cross this infor
types of M
• The protons that the bacteria and give
separated from the electrons flows not be co
through the exchange membrane. and desc
to provid
• It also prevents mixing of reactants in cating or
anode and cathode mation i
(www.mi
• if high concentration of oxygen is in
anode, electron will be consumed MFC Des
by oxygen
Many dif
• Can be a proton or cation exchange 2 and 3).
membrane. chamber
usually o
• if product at cathode is not water, separator
CEM can be a lot cheaper than (CEM) su
PEM salt bridg
choose a
FIGURE 1. Operating principles of a MFC (not to scale). A bacterium chamber
in the anode compartment transfers electrons obtained from an membran
electron donor (glucose)
5
to the anode electrode. This occurs either acceptor
through direct contact, nanowires, or mobile electron shuttles (small
 Cathode and equipment, in
for a paper that pr
• The electrons and protons this information. In
recombine at the cathode. types of MFCs, prov
and give examples
not be considered a
• Oxygen is reduced to water. and describe metho
to provide informa
• A platinum catalyst is used so cating or advancin
the oxygen is sufficiently mation is availab
reduced. (www.microbialfue

• Other reactants that are easily MFC Designs

reduced can also be used. For Many different con
example, Fe(III) can be 2 and 3). A widely
chamber MFC bui
reduced to Fe(II) usually of two bot
separator which is
• Bruce Logan introduces MFC
 (CEM) such as Nafi
https://youtu.be/ZotwUJAb8R4 salt bridge (27) (Fi
choose a membran
FIGURE 1. Operating principles of a MFC (not to scale). A bacterium chambers (the CE
in the anode compartment transfers electrons obtained from an membrane, PEM), b
electron donor (glucose) to the anode electrode. This occurs either acceptor in the cat
through direct contact, nanowires,
6 or mobile electron shuttles (small
H-configuration, th
 DIY: https://youtu.be/yDarDR4vi1A

Lab-scale
2014.igem.org

remediate polluted underground water and soil

Use soil as electrolyte www.theadvocateproject.eu

MudWatt: https://youtu.be/RdIV_UZFK9A

Different Kinds Of MFC 7

 Where Does Electricity
Come From?
• When microorganisms digest fuel (food), chemical bonds are broken. Some
of the released energy is transformed into electron that transfer inside cell.
• The electrons can be transferred outside cell via outer membrane
cytochromes, pili, and electron mediators that can cross cell wall and cell
membrane.

Miniaturizing microbial fuel cells, Trends in Biotechnology, Volume 29, Issue 2, February 2011, Pages 62–69
8
 E , , ~ = E’ - -In (n)
the substrate. The market for ion exchange membranes is nF
RT
E’ - - Chapter
constantly
= growing, (n)
In 3 Voltage
and more Generation
systematic studies are neces- Chapter 3 Voltage Generation
(3-2)
nF
sary to evaluate the effect of the membrane on performance
Gibbs Free Energy V.S.
and long-term stability (56). Potential
where E* is the standard cell electromotive for
T the absolute temperature (K), n the numbe
relationships
standard
Fundamentals for the
cellofelectromotive
Voltage electron
force,inRdonors
Generation = 8.3(substrates)
MFCs 1447 J/mol-K andC/mol
theacceptors (oxidizers).
gasis constant,
relationships
Faraday’s We therefore
for The
constant. the electron
reaction qud
review(K),
temperature
Thermodynamics
these relationships
n the
and the number oftoinelectrons
Electromotive
obtain
Force.
a better understanding
transferred, products
F=
andreaction of96,485
thebyboundaries
divided
review the
these onraised
reactants MFC
relationships to to
theio
• Electricity is generated an MFCElectricity
only if the overall is
operation.
day’s constant.
is generated in The
an MFCreaction
only quotient
thermodynamically is(ΔG
if favorable thereaction
the overall ratio
r<0, reaction).operation.
ofis theforactivities
r stands of the
thermodynamically
ed by the reactants favorable.
in terms of Gibbs
• Thefree
raised to The
energycan
reaction
theirreaction
expressed
can be
respective evaluated
stoichiometric
in unitsinofterms
be evaluated Joulesof n = product^]^
coefficients, or
(J),Gibbs free energy expressed in units
[reactants]‘
which is a measure of the maximal work that can be derived
of Joules (J), which is a measure of the maximal work that can be derived from
product^]^
from the reaction
The maximum(57, 58), calculated
calculatedas
electromotive 

force, Eemfithat can beBydeveloped inconvention,
any type of battery
the reaction, as The
the IUPAC maximum
(3-3) reactionsorare wr
allelectromotive f
fuel is
 given
reactants]‘ by
∆G ) ∆G0 + RTln(Π) fuel is given
so that the products by
are always the reduced s
r r (1)
species (oxidized species + e- + reduced spe
where • is ∆G
∆Gr (J)all ther is the Gibbs
Gibbs RT
free free energy
energy for the specificasconditions,
for specific
the standard conditions a temperatureRT of 298 K
convention,
conditions, ∆G•r0 (J)
reactions
E is, , othe
∆G is the
are
E’ - -
~ = Gibbs written
free
Gibbs
In (n)
energy
free
in the direction
underunder
energy standard
of chemical
standard liquids
reduction,
and 1 bar
conditions Edefined
for gases
usually E’(3-2)
, , ~(1=baras -Inatm
=-0.9869 (n
ducts are alwaysdefined the reduced n Fspecies, and the reactants are the oxidized n Fstandar
+
r
conditions usually298.15 as 298.15 K, 1 bar pressure, and with respect to that of hydrogen under
1edMspecies + e- forreduced
concentration
K, 1 bar pressure, and 1-1M -1
all species, species).
R -1
(8.31447
-1
AlsoJ mol
by IUPACK
concentration for all species,
) is convention,
= 0, referred wetotake as the “normal hydrogen elect
nditions where
the universal • R (8.31447 J mol K ) is the universal gas constant,
a temperature
E*constant,
gas of
is the standard T (K) K,
298is thecelland chemical
electromotive
absolute concentrations
temperature,force, R for= 8.3 of
1447
all chemicalsM
1 where for
J/mol-K E* the
is obtained
is the gas
with n = 1 relativ
constant,
standard cell el
and Π
ar for gases
T the(1absolute
(unitless)bar
is the= 0.9869
reaction atm = 100
quotient kPa).
n theAll
calculated as the ?I are
valuesofofelectrons calculated
In biological
• T (K) istemperature
the absolute temperature
(K), number T the systems
transferred, andtheFtemperature
absolute reported
= 96,485 potent
(K
activities of the• products divided by those of the reactants. because the cytoplasm of most cells isthe
at pH=
that of C/mol
hydrogenis under
ΠFaraday’s
(unitless) standard
is the conditions,
constant. The
reaction
The standard reaction Gibbs free energy is calculated from
whichcalculated
reaction
quotient is defined
quotient is to
asthethebe PC/mol
ratio ( Hof2 )the
activities is activities
of Faraday’s
the of
constant.
as the “normal
products hydrogen
divided
products by electrode”
the
divided reactants
by those(NHE).
raised
of theThus,
to theirthe means
standard
respective
reactants. that the adjusted
potentials
stoichiometric
If the reaction consumes potential

 byatthe
coefficients, 298or K is
tabulated energies of formation for organic compounds in products divided reactan
ls is obtained
water, availablewith n
r mole
from =of
many reactant
1 relative
sources to to aproduce
(59-61).hydrogen r mole of products, then Π is:
electrode.
cal For
systems the reported
MFC calculations, it potentials are usually
is more convenient pre-adjusted to neutral pH,
to evaluate
toplasm of most cells is at pH=7. For hydrogen, with 2H’ + 2e- + HZ, this
product^]^ product^]^
the reaction in n
terms=of the overall cell electromotive
Therefore,force
for n
E = E 0 - -RT
l n
(3-3)=
Z =H0 - (8.31
Oi

(emf), Eemf (V), defined [reactants]‘

as the potential difference between nF [H’I2
[reactants]‘ (2) (
adjusted potential at 298
the cathode and anode. This K isis related to the work, W
9
(J),
 pyrolyzed iron(II) phthalocyanine
2 or CoTMPP 2 have been 2
not all the
andard reaction Gibbs free
proposed as MFC energy 2 + is
Ocathodes
4H +
calculated
(54, electrode
+ 4 55). -
e ffrom 2 H2O reaction 1.229 pO2)0.2, pH)10 E0 (V)
to
tedbacteria.
energies of formation
Membrane. forTheMnO
organic 2(s)compounds
majority Hwhere
+ 4ofanode+
MFC Qf)
+ 2 designs
e-in Mn nF2+ +
require is2 the
H
the O+charge transferred
1.23 -[Mn in2+the
])5 reaction
mM, pH)
have been 2 HCO 3
- + 9 2H + 8 e - f CH 3COO + 4 H 2O 0.187 a

rrder
MFC Gibbs Free Energy V.S. Potential
available fromseparation
hat current
many sources
a CEM.it Exceptions
calculations,
carbon
O
of the anode2 + 2and
(59-61).
Fe(CN)
is more convenient 6
H +
3-
+

are naturally+ to -
-
expressed
the2cathode
e separated
O2 Oin+ Coulomb
e f H2compartments
cathode
f Fe(CN)systems
number
evaluate of
2
4-
4
6O2 electrons
+4H
H + + by
such
+ + as
4 e- (C),
f 2 Hwhich
4 exchanged
e- f 2 H2O
2O
0.361
pO2)0.2, [H2O
0.695 is determined
in the [Fe(CN)
reaction, 3-
6 ])[
by2] )
1.229 the
Fe(CN
n1.229
is the
5

action in termssediment
ally higher of the MFCs (37) or specially number
overall
a Calculated cell
fromelectromotive
designed single-compart-
Gibbs free energy forcedata ofMnO 2(s) + 4in
electrons
tabulated
+ + 2 e-b f Mn2+ + 2 H O
Hperref reaction
61. Note that mol,anand MFC
2 F with
is Faraday’
an1.23
acetat
ment MFCs-(30, 32). The most commonly usedOCEM is Nafion
2 + 2 Hcathode +×2 e10
+ - H)2O0.2, 0.695
Eemf (V), defined as3COO
CH theCo., ) 5 mM, pH
potential ) 7) and constant
an oxygen reducing(9.64853 (pf
4O2C/mol). 2 pH ) Combining
7) has a cell emf theseof two
0.805
act material (Dupont USA), difference
which is availablebetween from numerous
3- + e f Fe(CN)
- 4-
thode and •anode.
terials and For This(e.g.,
MFC
suppliers is related
Aldrichto
calculations, andthe
it is
Ion work,
more
Power, W
equations,(J), Fe(CN)
convenient
Inc.). we have to6 evaluate
Alternatives to the reaction
6 in terms 0.361
is available
ced by the cell, or overall
ofNafion,
the such ascell electromotive
Ultrex Calculated
CMI-7000 a(Membranes force from
(emf), Gibbs
E emf 
 free energy data tabulated in ref 61. Note tha
International b

ked carbon where Q ) nF is the charge CHare transferred

- ) 5 mM, pHin
3COOwell
the
) 7) and reaction,
an oxygen reducing the reaction,
cathode (pwe O2 ) can0.2,write
pH )

 Incorp., Glen Rock, NJ) also suited for MFC ∆G
)expressed
beads (35, WapplicationsEemf Q ) (6)-
in
and
Coulomb
∆G are
(C), which
r considerably more (2) is determined by the
cost-effective than E ) -
r
(3
mportant to number
Nafion. When ofaelectrons
CEM is used exchanged
in an MFC, initthe reaction,ton is
is important
emfthe
nF O2 + 4 H+
m growth or • number
recognize
wherethat Qof=itelectrons
may
nF is be per where
thepermeable
chargereaction Qto ) mol,nF and
chemicals
(electrons)
is the suchcharge
F is
transferred as transferred
Faraday’s in the
in the reaction,
reaction,
the
ces has not constant
oxygen, (9.64853other
ferricyanide, × 10 expressed
4 C/mol). in
ions, or organic Coulomb
Combining
matter used(C),
these
as by which
two is determined by the
expressed in Coulombnumber (C), If of
whichallelectrons
reactions
is determined are evaluated
the number at standard
of n is Ethe conditions
) 0
theequations,
substrate. The we have
market for ion exchange membranes is exchanged in the reaction, cat E cat -
nt chemical electrons
constantly exchanged
growing, and morein Π)
the
number
systematic 1,
reactionthen
of studies
electrons are per
neces- reaction mol, and F is Faraday’s
k et al. (31) sary
• ntoisevaluate
the number the effect
of of theconstant
electronsmembrane per (9.64853 ×mol
on performance
reaction 104 C/mol). Combining these two
∆Gr
ently linked and long-term stability (56).E equations, )- we have (3) ∆G A variety
0 of catholytes has
emf 4
the anode. • F is Faraday’s constant (9.64853 nF × 10 C/mol). 0 r
the cell voltage varies. For
E ) - (4
composites Fundamentals of Voltage Generation in MFCs emf
∆Gr nF
ferricyanide have been use
A va
emf ) -
generation • Combining If all equations
Thermodynamics reactionsand the ofElectromotive
are Qevaluated
and ΔGr,atwe Force. have:
standard Econditions,
Electricity (3)solution
nF pH of the cathode
metabolites is Π ) 1, then
generated in an MFC only if the overall reaction is the
where E emf (V) is the standard cellcathode
0 potential.
electromotive force.UsingWe
ferri
• Ifthermodynamically favorable.
all reactions are evaluated at The reaction
standard can be evaluated
conditions, Π = equations
1, then wetohave
potentials available
material can in terms of Gibbs freeoenergy expressed can
If alltherefore
reactions
in units of use
arethe
Joules above
evaluated
(J), at standard express
conditions, thefor inor
overal
pH o
standard Eemf, or E emf:
 reaction 0 different conditions, itcath ca
nd that flow which is a measure of the Π
maximal
0
) 1,
work∆G
then r in
that canterms of the potentials
be derived as
node, and from the reaction (57, 58), calculated Eemf ) - as (4) cathode potential for these pote
nF 0.361 to 0.805 V.
ased power 0 diffe
∆G
0 RT The cell emf is calculat
urface area) • Therefore, from ∆Gr ) ∆Gr + RTln(Π) , we have:EE0emf
0
(1)))-Eemf - r ln(Π) (4) (5
cath
he increase where E 0
emf (V) is the standard cell electromotive emfforce. We
nF nF
0.36
ion into the can therefore use the above equations
where ∆Gr (J) is the Gibbs free energy for the specific to express the overall Eemf T)
could have reaction∆G
conditions, in r0terms of the
(J) is the Gibbs potentials
where E0emfas
free energy
The under
advantage
(V)
10 is the standard
of eq 5 cell
standard is that it is positive
electromotive for We
force. a favorable
de as well.
 Half Cell Values fromThis
reaction. 57; All
Ref calculated
emfPotentials Are
nFShown
RT an against
emfprovides NHE) for the aspotential
listed in Table 1 would produce
that thesignificantly usingdifferen
Eemf emf
) E0emf - upper limit
ln(Π) (5) reaction as reduction
is occurring). Note reaction (although
result an10oxi
eq e
ectrode cell voltage; the actual potential
reaction nF
derived from the
E0 (V) MFC will voltages,
thatreaction
of eq is
conditions and thus
3 occurring). different
and eq 5 only Note levels
if that of
EMFCthe
the pHpower
(V) result output.
at theusing anode The 10p
eq an
be Thelower due to various
advantage of eq 5potentialis that it islosses positive (seefor below).
a afavorable - produced
that ofare
cathode eqbyequal.
3anand MFC eqtherefore
Equation 5 only10 if depends
the pH at
demonstrates onthe thethat
choice
anode usin ao
node 2 HCO - + 9 H+ + 8 e- f CH COO- + 4 H O 0.187 HCO )5 mM, CH COO -)5 mM, pH)7 -0.296 b
Standard
reaction, 3
The and Electrode
advantagedirectlyofproduces Potentials.
eq 3
5 is that a it The 2 reactions
is positive
value of the for emf occurring
a favorable
for the 3 cathode,
samecathode anode
3 and this
areinequal. a system should
Equation with be10 taken
demonstrates
different into
cathode account
that
condiusw
athode
in
or
cell
MnO
the
reaction,
reaction.
O2 + 4 H+This
the
reaction.
O2cell
voltage; Example Of ECat And EAn
O2 + 4 H+ + 4 e- f 2 H2O
MFC+can
separate
+ 2voltage;
cathode.
be
Standard Potentials
lower H+due
and
4e
This
the
According
E
+2e
and
be
-
+ actual
2(s) + 4 H + 2 e f Mn
tothe
- f
analyzed
directly
calculated
reactions
calculated
various
H2O
- potential
actual
to2 the
Theoretical
in termsaofvalue
produces
f 2 H2O emf provides an upper
occurring
emf
2+
potential
potentialIUPAC
H2O at the
+ provides
2 derived
Potentials
derived
losses
the half
an
from
convention,
for
(seefrom
1.229
cell
of1.229
the
anode
upper
1.23
reactions,
emfforpO
limit
the limit
the
below).
0.695
Typical
MFC and[Mn
MFC
standard
pO2)0.2, pH)7
forthe
the
for
will
pO2will
Conditions
the as
2)0.2, pH)10
the
2+])5 mM,

)0.2, [H
in
comparing
same
listedanode
asOpen
voltages,
dynamic
produced
listedand
pH)7
voltages,
in Table

2O2] ) 5 mM, pH)7

MFCs
produced E
power
Circuit
and
value
by
(E
4-]by
in1awould
thusVoltage
in Table
thus
anthat
MFCan
MFC
Was
densities

MFC
system
1 would(OCV).
different
different
does
produce

not take
therefore
Calculated
therefore
achieved
with
produce
levels
levels
0.805b
different
0.627
ofThe
0.470
into
depends
0.328
by different
significantly

of account
Using
depends
power
Eq
cathode
celloutput.
significantly
power emf isdiffere
on output.
5
theinternal
choice
on account
the choice
MF
con
differen
a the
The
The
p
loo
be lower
Standard
potentials
Fe(CN) 6
3- + 0due
(at fto
eElectrode
-298 K,various
Fe(CN) 1 bar, potential
6Potentials.
4- 1 M) areThe losses
reported reactions(see
as abelow).
0.361 reduction
occurring [Fe(CN)63-])[ The
cathode, open
Fe(CN) MFC6circuit
and this voltage should (OCV) be is0.361the cell
taken intovoltage that ca w
Cell Valuesin from Ref
Standard 57; All Potentials
Electrode Are
Potentials. Shown The against
reactions NHE) occurring cathode,
comparing and
powersome this
densitiesshould be
achieved taken into
by different MF account
theGibbs
Calculated potential,
from MFCi.e., canthe
free be
energyanalyzed
reaction isinwritten
data tabulated termsinof as
ref the 61half
consuming
. b Notecellthat an MFC with measured
reactions,
electrons an acetate oxidizing after anode time (HCO3- in ) 5the mM,absence of cur
COO- ) 5 mM, or in
(57). •
the
pHtheAnode:

For MFCand can
)separate
7)example, beifanalyzed
an reactions
oxygen
reaction acetate
reducing in
occurring terms
iscathode
oxidized (of
atpOthethe
2 by half
anode
) 0.2,bacteria
E0 pH cell
(V) ) and reactions,
hasthe
7) at
• Cathode:

a cell emf comparing
of Open
Theoretically,
0.805 -Circuit
conditions0.296) power
the Voltage
1.101OCV densities
V. should (OCV). achieved
The
approachEMFC cellby
(V)emfdifferent
the is cella theM
em
or the
cathode.
anode ifwe acetate
write is
separate
According the oxidized
to the by
reactions
reaction asbacteria
occurring
IUPAC atatthe
convention, the anode standardand the if wedynamic consider
practice, Open value Circuit
thethat
however, case Voltage
thewhere
does not take
OCV (OCV).
isoxygen intoThe
substantially iscell emf
account internal
lower is tha
a th lo
2 HCO - + anode,
3cathode.
potentials +
9 H (at +According
8
the
298 -
e reaction
K, f1CH 3COO
to
bar, 1the
is:
 -
M)IUPAC+are 4H 2Oconvention,
reported 0.187 a
as a reduction HCOused
standard 3 )5The
- mM,
celldynamic
as open
emf,
the CHdue COO
value
3circuit
electron -
to various)5
that
voltagemM,
does
acceptor pH)7
not for
(OCV)
potential take
islosses.
the -0.296
into cellaccount b
Forvoltage
example,internal
that ca
a ty
ere QO2)+nF 4H is
+ the
+ charge
- transferred in the reaction, the reaction,
pO2)0.2, we can write b
potential, 
 4 ei.e.,f
potentials (at -2298
the H 2O K,+ 1 bar,
reaction -1 M) are
is written asreported
consuming- 1.229 as aelectrons
reduction reaction, pH)7we can
The
measured open circuit
after
potential
write:
 voltage
some of atime (OCV)
cathode is
in the the
using 0.805
cell
absence voltage
oxygenofat cur that
pH
pressed in
O2 +(57).Coulomb
4H + 2HCO (C),
+
 4 example,
-
e i.e.,3 2the+
which 9H
H2if O is + 8e
determined f CH by COO the
by 1.229
+ 4H O atpO
(6) 2)0.2,Theoretically, pH)10
measured after some time 0.627
mberMnO
potential,
of electrons
For f
exchanged
reaction
in
acetateisiswritten
the reaction,
oxidized
n
3 as consuming
is the
bacteria 2 electrons the 
 O about 0.2
+ V. This -
theisOCV clearly lowerin
should than the
approach the absencethe cell
expected ofval
emc
2(s) + however,
(57). 4weFor+ +
H write 2 ethe
example, - Mn
thefstandard
2+
if acetate + as2 His2Ooxidized 1.23 TABLE 1. [Mn 2+
the])52practice,
at Standard +
mM, 4 H pH)7
Potentials
Theoretically, + 4 e f
E0the 2
and H OCV O
2Theoretical
should (8)
0.470
Potentials
approach for cell
the Typic
thaae
anode
mber of electrons per-reaction
reaction
mol, and potential F is Faraday’s for by bacteria

 0.805 V, however,
indicating thethe OCV
large isenergy
substantially lower
loss occurring
O2 + The2H + + 2 we e f H2Othe 0.695 pOCell 2)0.2, [Hpractice,
O2from] )due 5Ref mM, 57; pH)7 Are0.328
two to and Half Values All Potentials Shown against
anodestandard write
potentials reaction
are as
reported cell 2emf, however,
toenergy
various the OCV
potential islosses.
substantiallyFor toexample,lower athty
theserelative the normal
2 cathode. This loss is often referred as overpote
nstant (9.64853 reduction
× - 104 C/mol). is written Combining as*:
 
 RT 1
Fe(CN)
uations, wehydrogen
ated from standard
6

Gibbs
3-
have
+
TABLE
e

 2HCO
1.
free2HCO
f Fe(CN)
electrode
3
-
conditions
Standard
energy
+
3
-
9H
+
data
4-
(NHE),
6+
(298
9H
+ 8e
+ K, pH
Potentials +
tabulated
which
-

8e
f
E
CH hasCOO
- 2 ) 31 bar,b [H
0 fand
in CH
a potential
Theoretical
ref 3 COO
61 .
-
+
0.361
Note
4H
+ 4H
2
of
that
O
-+] )electrode
1 M).
Potentials 2 O
an
[Fe(CN)
zero(6) at Ecat
To(6)
for
MFC Typical
with
3- ])[
cell
6 measured
or) the
about
0 Fe(CN)
emf,
Ecat difference
measured 0.2 4F
Conditions
conditions
an acetate
due
- potential
V.and (
6ln
4-

This
in
]
to
potential
pO
MFCs
various
the
oxidizing
between
[H )
+
is2reaction
clearly
E
actual
4
anode
MFC
potential
of a cathode the
]of (Ea lower
cathode
Was
potential,
MFC (HCO
losses.
than
3
using
potential 0.361
Calculated
- ) the
which
5
For
(9) under
using
example,
oxygenequilib
oxygen
expected
mM, Using
for
at pH
Eq
this 5
a
Eval
at 0p
ca
(
) 5 mM, pHobtain ) 7)andand E o = 0.187
Half
the Cell
antheoretical
oxygen Values
TABLE ∆GV1. from
anode
Standard
reducing Ref 57;
potential,All(pPotentials
Potentials
cathode O2 E )An
E , under
and
0.2, Are
pH )Shown7) hasagainst
specific
Theoretical
anode aPotentials cell 2emf o about
0.805
NHE)
0.605
HCO for
of V, 0.2
V-Typical
0.805 (0.805
+ 9-V.
indicating
H
This
+ V+ -
Conditions
0.296) 8
isthe clearly
1.101
e0.2
- f large
inV.
V). CH
lower
MFCs
Thisenergy
COO E than
(Eloss
illustrates
- + 4
theoccurring
H
expected
WasOthatCalculat
the
0.18
va
The 0 • E for this
3 reaction is 1.229 V
3 MFC MFC 2
•standard potentials 5,are reported relative tothe
Athe normal
r 0.805 V, indicating the
conditions, The Eemf we)
standardand- Half
use eq Cell
potentials, Values
with theE
o
from
, are Ref
activities (3)57;ofAll
reported variety
Potentials
different of Are catholytes Showncathode. has
against
application been
This used,
NHE)
of - fand
energy
thermodynamic loss forislarge
each
often ofenergy
these loss
referred
calculations to as occurring
is overpote
to identif
hydrogen electrode
The standard electrode nF
potentials
(NHE), are
which reaction
reported has a relative
potential the cathode
to ofthe zero
cell normalat
voltage E 0 O(V)
2
varies. + 4
cathode.
For H + + This
example,4 e energy 2
manganese H
conditions2
lossO is often
oxide referred
and to as MFC 1.22
Eoverpo(V)
species assumed to normal
be equal to their electrode concentrations. For or
size the and difference
nature ofbetween
energy the
losses. potential under equilib
hydrogen relative to the
electrode
electrode (NHE), hydrogen
which -has [Hreaction
a potential • Another Obeen +4 commonly +
E+
H difference
(V)
-
4alternatives
e used f 2 Hreactant 2O is Theferric under equil
conditions 1.22
8)e1 4ofH2zero
)+1reaction, at0.187
+] ferricyanide 2aor
) nF is standard
the
acetate charge
anode conditions
oxidationtransferred
2 HCO (298
(Table
- in
3 +
K,
1),9H pH
the
we
+ reaction,
+2therefore fbar, CH 3COOthe
have
- M). OTohave can the
weconditions used
write
HCO 0as
3 and
- )5 mM,the between
actual
CH 3COO
to potential,
oxygen.
-the
)5 potential
mM, which for
pH)7 this bca
-0.296
standard (NHE), which
conditions has a+potential
(298 4K, -pH )of 1zero
bar, ,at[H-pH+] ) 1 M). To cyanide, MnO 2(s)whose+)0.2, +
4 Hreduction + the -
2 eaffecting freaction the +
2+
Mnpotential, 2 H2O
is:
 1.23
dIf in
all Coulomb
reactions
obtain are
theevaluated
cathode
(C), theoretical
which O2 is
anode +at4determined
Hstandard
anode
+
2 HCO fconditions,
epotential,
-22by
+ H9 2O the
H E+An + under
8 e f +ofspecific
CH
the cathode
COO - 1.229 + 4
solution
conditions
0.605
Identifying
H O pO
V can
2 also
(0.805
0.187 and
a pH)7
Factors Vvary,-HCO 0.2
that actualV).
-)5
DecreaseThis
mM,
overall
CHillustrates
Cell
COO which
-)5 that
Voltage for
mM, this
0.805
the
pH)
b
) 1, then conditions,
obtain standard
the conditions
wetheoretical
O2 the +
eq4 5, (298
+anode
+O
Hreaction, 4 e+
3
K,activities
pHH2
- potential, =1 Ebar, of,2the[H ] specific
under
cathode 3
potential. 
 +
2 2 pO
Oapplication
Using
+
HV2+ +
eq
)0.2,
-
2 epH)10 f
of9-4thermodynamic
and H
- 2O
3
tabulated standard 3 0.69
of electrons exchanged use
in
cathode with the
2+ 4 H
f n2+-is +2Othe
4 e-- fAn
H2Odifferent 1.229 O
2 0.605
+ 4 H 1.229(0.805
+ e -VpO
f 22
0.2
)0.2,
H
2 V). This
O pH)7 illustrates
calculations (8)
0.627
is tothat
identifthe
+
( ) Fe(CN) 3- e f Fe(CN) 4- 0.36
=1
conditions,
species M).
assumed MnO
we to use (s)
2 eqequal
0be
+ 4 H
5, Owith
RT +to+
4[CH
2
the e 3+COO
H+ activities
their f Mn 2+
] 2ofH2the
+
4concentrations.
potentials
2 H O
O2 different For

available 1.23 The
2for
size maximum
inorganic
[Mn
application
and
2+ ])5 attainable
compounds
mM,
1.229 of thermodynamic
6 nature of pO pH)7
energy 6MFC
(57)
2 for voltage
several (emf)
calculations is to iden is theoret
0.470
of electrons per reaction mol, and + +F 2 is - Faraday’s
e- f 2)0.2,losses. pH)10
species E
assumed )O E + to
02 -
Hbe1), ln
2
equal e f to +H O
their 2 2+concentrations. different (7)
conditions,
2+ +For 0.695 onsize it
the pO
can
order )0.2,
be [H
seen
ofenergy
1.1O ]
that)
2Venergy 5
(see mM,
the
2+])5above). pH)7
theoretical However, the 0.328
meas
(9.64853acetate 4 oxidation
× •10Therefore, C/mol).
0
An (Table
∆G
2 An
theCombining
Fe(CN) r 8F
theoretical
3- +
MnO
e
we
-
therefore
(s)
these
[HCO
2
anode
Fe(CN)
2 -
4 H
two
] [H
have
+
reduction
4-
+29e- f aMn
] Calculated 2 
 H 2Ofrom
0.361 Gibbs and 2 nature
1.23
[Fe(CN) free
RT 3- ])[
2 of
[Mn
Fe(CN) 1data 4- ]
losses.
mM,
tabulated pH)7 in ref 61 . b Note
0.361
s, we have
acetateEemf
potential,
a Calculated from
) - (Table O
oxidation
E nF
, under
6

An Gibbs free
1), fwe therefore
specific
+ 3
2 + 2 H + 2 e f H2O
Fe(CN)6 + e f-Fe(CN)6
energy 3-
6
conditions
data
(4)
-
- have

tabulated
cathode
CH
0.361
is: 

in 4- to
ref
potential
2 3COO ) 
 5 mM,
-
0.805
61 . V.
Ecat
for
MFC pH
these
) voltage
Identifying
InIdentifying
b Note that an MFC with
an open
different
E)0cat7)0.695
-and
0.361
isan
Factors
4F
6

(
Factors
circuit, an
catholytes
considerably
lnoxygenpO
when
pO
that
[Fe(CN)
2)0.2,

2that
acetate [Hno )
6
+
[Hrange
lower
Decrease
reducing
6 ]Decrease
3-4
current
])[ Fe(CN)
oxidizing
)from
due
2O2] cathode Cell
5 mM,to Voltage
Cell
a(9)
(number
pH)7
pO2 ) 0.2,
6 ] Voltage
is flowing,
anode 4- (HCO the maxim
- ) 5 mM
of lo
p

n therefore Ethe
o case
use
CH

=
An the
Eemf
3
ere E0emf (V) is the standard
COO

Eabove
- ) 5 mM, pH ) 7) and an oxygen
For the theoretical
owhere
EAn )
∆G
EAn
CH
) -equations
) nF
cell
3COO
0
a Calculated

r) -EAn
oxygen
- from
)to
RT
cathode
EAnelectromotive
0
5-
is 8F
mM,
ln potential,
RT
usedpH
express ln
8F [HCO
[HCO ((
[CH3COO
Gibbs
as)the
[CH
force.
the
reducing
3COO
free
- 2We
Eenergy
electron
7) overall
3and ] -[H
(3) ]
cat, if] we
+

[H
9 ))
] - cathode
] + acceptor
an2 oxygen A9where
]
The
reducing
variety
expressed
(pcell
consider
data tabulated
O 2

Qfor
) emf
(7) in on
(7)
ofcathode
0.2,

)catholytes• nF
is
pH

EMFC
in the
The
MFC
refThe
7)maximum
calculated
)

generation,
o is
Coulomb
O2the
pon
(for
E emf
)
has
voltage
61. maximum
the
the
this 0.2,
has
)
voltage
a as
cell
order of 1.1
b Note that

charge
pH
order
E
emfattainable
achieved
voltages
been
reaction
cat
(C),
of

)considerably
is- 7)used,
of E has
an
1.1
which
0.805
attainable
an V (see
MFC
thus
isachieved
transferred
aV cell
-

(see
and
0.361
is
MFC
with
0.296)
far
MFC
above).
emf
forVof up
voltage

in
above).
lower each
1.101
is 0.80
voltage
an acetate
tothe
0.805
due now
(10)
V.
However,
-to
(emf) 3is theoret
Voxidizing
(62).
However,
of
(emf)
aremain
reaction,
0.296)
these
During
isanode
the
1.101
number the
theore
meas
below
V.
me
of
cu(H
lot
ction in termswhere of theQpotentials nF is as the charge transferred 3 in thethe reaction,
cell voltage InMFC reaction,
varies.
an openvoltage
Forcircuit,weiscan
example, considerably
write
when no determined
manganese loweroxide
current isdue to
flowing, by
and the
a number
the maxim of
VOL. 40, NO. 17, 2006 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9
expressed
For the theoretical in Coulomb (C), which is determined number by the of electrons Inisan exchanged
open circuit, inthus
when the no reaction,
current nThe
isVflowing, is During
the the max
*According
number to of where
the IUPAC
electrons Qcathode nF ispotential,
)exchanged
convention, the in charge
standard
the
Ecattransferred
, if ferricyanide
reaction,
we
where consider
potentials
n
the
is in minus
the the
(at have MFC
sign
reaction,
298 been
K, avoltage
1 used
result
bar, the
1ofachieved
as
M)the alternatives
definition
reaction,
are + we can
reported far
of to
the
-as
iswrite
0.80
oxygen.
anode
a (62).
reduction cu
For the0theoretical cathode aspotential, Ecat,acceptor
ifnumber
we consider of reduction electrons MFCreaction voltage Oalso + vary,
achieved 4 achieved
Hmol, +
thus 4andefar fis 20.80
isH OV remain
(62). During (8)c
reactionsthe arecase
potential, E evaluated
number
where
)
i.e.,Eof the - atRTstandard
oxygen
expressed
reaction
electrons ln(Π) isin
per
used
is
conditions,
Coulomb
written
reaction
the (C),
as
mol,
electron
(5) which
consuming
and F
pH
potential
is
of thefor
isFaraday’s
determined
electrons. cathode
as the percan
generation,
bysolution reaction
voltages 2(although affecting
an up Fto
the
oxidation now Faraday’s
2overall below
en the case where nF
emf emf oxygen is used as the electron acceptor
constant
reaction
cathode for
(9.64853
ispotential.
occurring). generation,
Note× 10
Using that 4 the
eq voltages
C/mol).
9result
and achieved
Combining
using eq 10up
tabulated to
equals now -
these
standard
+ remain
two belo
number of electrons exchanged in the reaction, n is the + 4 H + 4 e 2 H
O f 2O 9
constant (9.64853 × 10 C/mol). Combiningthat 4 these 11 two
of eq
equations, 3 and weVOL. eq
have 540,only NO. if 17,the2006 pH / ENVIRONMENTAL
at 0the anode RT2 and 1the & TECHNOLOGY
SCIENCE
 Theoretical EMFC
• Therefore, from discussion on p. 5 and p.6, we know that theoretically, we can get
voltage output from a MFC:

EMFC = ECat - EAn
• EMFC represents the total energy contained in the electrochemical reaction in anode
and cathode
• minus sign of EAn is a result of the definition of the anode potential as reduction
reaction (although an oxidation reaction is occurring)
• the following table demonstrates that using the same anode in a system with
different cathode conditions would produce significantly different cell voltages, and
thus different levels of power output. 


TABLE 1. Standard Potentials E0 and Theoretical Potentials for Typical Conditions in MFCs EMFC (EMFC Was Calculated Using Eq 5
and Half Cell Values from Ref 57; All Potentials Are Shown against NHE)
electrode reaction E0 (V) conditions EMFC (V)
anode 2 HCO3- + 9 H+ + 8 e- f CH3COO- + 4 H2O 0.187a HCO3-)5 mM, CH3COO-)5 mM, pH)7 -0.296b
cathode O2 + 4 H+ + 4 e- f 2 H2O 1.229 pO2)0.2, pH)7 0.805b
O2 + 4 H+ + 4 e- f 2 H2O 1.229 pO2)0.2, pH)10 0.627
MnO2(s) + 4 H+ + 2 e- f Mn2+ + 2 H2O 1.23 [Mn2+])5 mM, pH)7 0.470
O2 + 2 H+ + 2 e- f H2O2 0.695 pO2)0.2, [H2O2] ) 5 mM, pH)7 0.328
Fe(CN)63- + e- f Fe(CN)64- 0.361 [Fe(CN)63-])[ Fe(CN)64-] 0.361
aCalculated from Gibbs free energy data tabulated in ref 61. b Note that an MFC with an acetate oxidizing anode (HCO3- ) 5 mM,
CH3COO- ) 5 mM, pH ) 7) and an oxygen reducing cathode (pO2 ) 0.2, pH ) 7) has a cell emf of 0.805 - 0.296) 1.101 V.

12
 Voltage Loss
• Theoretically, the open circuit voltage
(OCV, voltage measured by connecting
anode and cathode to a multimeter) of
results in

a MFC should approach EMFC activation losses
• However, OCV is always lower than
EMFC. EMFC

• Why?
• Voltage is lost at cathode and anode
even when current is not flowing nutrient
mass transfer

mass transfer
 of cell waste
• This energy loss is often referred to of nutrient
as overpotential, which is resulted
from several losses:
1. activation losses;
2. bacterial metabolic losses
3. mass transport or slow mass transfer 

concentration losses 

reaction
no reactants on surface 2011.igem.org
13
ly, can be written as
2.2.2. Transport-related resistances
2Hþ þ 2e/H2 (R1) These are the physical resistances experienced in

Voltage Loss
V (35). In general, the difference between the measured cell
1
voltage and the cell emf is referred to as overvoltage
2OH" / O2 þ H2 O þ 2e (R2)
process such as gas bubbles covering the electrod
present in the electrolyte solution, resistances to the
and is
in the electrolyte and due to the membrane used for
the sum
2 of the overpotentials of the anode and theHcathode,
2 and O2 gases. Rbubble;O2 , Rions, Rmembrane and
erall and the
chemical• ohmic
Except loss
reactionfor of the
the system
ofoverpotential,
water additionalcan
electrolysis voltage
be losses appearaswhen
considered current
transport is running:
resistances.
Both electrical resistances and transport resistan
Ecell ) E emf - (Σηa + |Σηc| + IRΩ)
EMFC (11) according to the Joule’s law [37]
generation
1 phenomena [40] and thus inefficiency of the elect
þ O2 • η: overpotential
 (R3)
2 where Σηa and |Σηc| are the overpotentials of the anode The lost energy due to these resistances is also know
and
a: anode

the cathode c:cathode
respectively, and IRΩ is the sum of all lossohmic
[41].
cal circuit
lossesanalogy
which ofare water electrolysis cells
proportional to the generated current (I)
and ohmic• resistance
RΩ: ohmic of the system (RΩ). The overpotentials
resistance
 2.2.3. Electrochemical reaction resistances
electrochemical reaction
of the electrodes areprocess
including loss oftovoltage
generally proceed,
currentto acircuit,
number
dependent The
electrolyte,
and reaction
membrane,
in an resistances
and otherare due to the overpotent
resistances
have to be overcome, requiring a loss
sufficient overcome
2 the activation energies of the hydroge
MFC they canthat cause
roughly beohmic
categorized aselectrical
or Joule heating(i)(=I
follows: R)
activation
pply.losses;
These (ii)
barriers formation reactions on the cathode and anode s
• include
bacterial
R1 and electrical
metabolic resistance
losses;
R’1: electrical and of the
(iii)
resistance mass
of thetransport
circuit
ctivation energies of the electrochemical reactions directly cause the increase in the overall cell potentia
or concentration losses
• Rbubble (see below).
: resistance from non available electrode surface 

on the surfaces of the electrodes, availability of electrode inherent energy barriers of the reactions, determini
In MFCs the measured due tocell voltage
partial coverageis usually
by gasofa linear
bubbles or impurities
the electrochemical reactions [42].
ue to partial coverage by gas bubbles formed and the
function of the
• Rcurrent (see discussion of the polarization
ions: resistances to the ionic transfer within the electrolyte solution
curve below), and can be described simply as
• Rmembrane: resistance to the ionic transfer cross the membrane
e
Ecell ) OCV - IRint + - (12)

where IRint is the sum of all internal losses of the MFC, which
are proportionalR1 to the
Ranodegenerated
Rbubble,O2current (I) andRinternal
Rmembrane ions Rbubble,H2 Rcathode R’ 1
resistance of the system (Rint). A comparison 14 of eqs 11 and
es which are proportional to the generated current (I)
ohmic resistance of the system (RΩ). The overpotentials
e electrodes are generally current dependent and in an

Voltage Loss
C they can roughly be categorized as follows: (i) activation
es; (ii) bacterial metabolic losses; and (iii) mass transport
oncentration losses (see below).
n MFCs
V (35). the measured
In general, thecell voltage between
difference is usuallythea linear
measured
Maximum cell
power transfer theorem
tion of the• current
When (see discussion weof the polarization
voltage and the analyzing
cell emfaisMFC,
referred usually
to asuse
overvoltage and power
maximum is transfer theorem states that, to
e below), and can beequation
following described simply as
for simplification obtain maximum external power from a source with
the sum of the overpotentials of the anode and the cathode,
purpose: a finite internal resistance, the resistance of the load
and the ohmic loss of the
E ) OCV - IR system (12)
must equal the resistance of the source as viewed
cell int
from its output terminals. Moritz von Jacobi
re IRint is the sum Ecell )E
of all emf - (Ση
MFC
internal a +of
losses |Ση + IRΩwhich
c| MFC,
the ) published (11)the maximum power (transfer) theorem
around 1840; it is also referred to as "Jacobi's law”.
proportional to the generated current
• Part of overpotential is not current (I) and internal
The efficiency of power transfer to the load is
where
tance of Ση and |Ση(R
thea dependent,
system are
c| int
and the
). A overpotentials
comparison
this is included in ofOCV.
eqsof11
theand
anode and
defined as:
thethat
hows cathode respectively,
the overpotentials
When andanode
of the
the overpotential isIR Ω is thethe
and
current sum of all ohmic
cathode
losses
occur which
under open arecircuit
dependent proportional
(mass transfertoor
conditions the
are generated
included
concentration), currentFIGURE
in the (I) 4. Electrochemical analysis of microbia
e and
of OCV in iseq 12, while Anodic (blue solid line) and cathodic (red dash
ohmic itresistance
included thethe
ofinternal
in systemcurrent
(RΩ). dependent
resistance. The overpotentials
profilesisover
The efficiency time when
only 50% whenmaximum
applying power
the current inte
potentials of
of the electrodesthe electrodes
are generally and ohmic
current losses of
dependent theand in an
• Using the simplified equation, MFC systems transferdetermination
is achieved, but ofapproaches
the ohmic resistance
100% as theof an MFC
emMFCare they
captured
can in
roughlyIR int . MFC systems
be categorized that
by and showasafollows: are well
maximum(i)load activation
are well described 3 indicate
resistance the voltage
approaches differences
infinity related to the o
(but power~0
ribed by eq 12 show
losses; (ii) bacterial
power output a maximum
metabolic
when the losses;power
internal andoutput when
(iii) massbecause
resistance, transport
sections 1 and
current~0 when 4 indicate voltage losses caused b
R—>infinity)
nternal resistance, R
Rint, is equal
or concentration , is equal
int to external
losses to
(see below). external resistance,
resistance, Rext overpotentials. (B) Cyclic voltammogram (solid l
(52). In
Although
MFCs Rintmeasured
the includes morecell than just
voltage is ohmic trochemically active mixed microbial community. T
• MFC performance can be assessed in usually a linear
tance (RΩ), both terms are often used interchangeably connect the oxidation and reduction peaks o
function ofterms
the ofcurrent (see discussion
both overpotentials of the polarization
and ohmic
MFC researchers should be aware
OCVof the differences in compounds (6).
curve below), and
losses or incan beofdescribed
terms and simply as
internal
e two terms. MFC
lossesperformance can be assessed in terms
oth overpotentials and ohmic losses or in terms of OCV maximize the MFC voltage, therefore, the p
internal losses, based on Ecell ) OCV
various - IRint discussed
techniques 15
(12)
anode should be kept as low (negative) as poss
 the sum of the overpotentials of the anode and the cathode,
and the ohmic loss of the system

Power Curve / Polarization Curve

Ecell ) Eemf - (Σηa + |Σηc| + IRΩ) (11)

where Σηa and |Σηc| are the overpotentials of the anode and
Rext
the cathode respectively, and IRΩ is the sum of all ohmic
changing from
losses
• From the which
above are proportional
equations, we cantoeasilythe generated
obtain current (I) 1Ω to 10 MΩ
internaland ohmic resistance
resistance of thecurve.
from power systemIt(Ris Ω). The overpotentials
equal to the
of the electrodes are generally current dependent and in an
resistance
MFCof external
they loadbe
can roughly when maximum
categorized power(i)isactivation
as follows:
produced.
losses; (ii) bacterial metabolic losses; and (iii) mass transport
or concentration losses (see below).
• Meanwhile, In we
MFCs canthe
also get polarization
measured cell voltage curve to seea linear
is usually
V
function
(35). In general,
of the current
the difference
(see discussion
between
of the
the measured cell
polarization Ag/AgCl
what kinds ofvoltage
resistance
and
dominate
the cell emf
the
is
power
referred
output
to as
of
overvoltage and is ref. electrode
MFC. curve thebelow), and can be described simply as
sum of the overpotentials of the anode and the cathode,
and the ohmic E loss of the
) OCV - system
IR (12)
cell int

where IRint is the sum Ecell ) internal

of all MF - (Ση
Eemf a +of
losses |Ση + IRΩwhich
c| MFC,
the ) (11)
good cathode
bad cathode are proportional to the generated current (I) and internal
where
resistance of Ση
thea and |Ση(R
system are
c| int ). Athe overpotentials
comparison of eqs of11
theandanode and
thethat
12 shows cathode respectively,
the overpotentials andanode
of the IRΩ isandthethe sum of all ohmic
cathode
losses
that occur which
under openarecircuit
proportional
conditions toare
theincluded
generated currentFIGURE
in the (I) 4. Electrochemical analysis
Anodic (blue solid line) and cathod
= Rextand
Rin value ohmic
of OCV inresistance
eq 12, while of thethe system (RΩ). dependent
current The overpotentials
profiles over
overpotentials of the electrodes
of the electrodes are generally and current
ohmic losses
dependent of theand in an
record voltage (V)time
andwhen applying the
determination of the ohmic resistanc
systemMFCare they
captured in IRintbe
can roughly . MFC losssystems
categorized asthat
follows:are well
(i) activation
calculate current (I) and power (P)
3 indicate the voltage differences rela
described by (ii)
losses; eq bacterial
12 show slope
ametabolic
maximum
= RΩ power
losses; output
and (iii) when
mass when different1 loads
transport
sections and 4 are applied
indicate voltage los
the internal resistance,
or concentration lossesR , is
assuming
int equal to
(see below).
current external
dependent 
 resistance, I = V/R
overpotentials. ext(B) Cyclic voltammog
Rext (52). In
Although R includes
overpotential more
can be than
neglected
MFCs the measured cell voltage is usually a linear
int just ohmic P=V 2/R
trochemically active
ext mixed microbial
resistance (R
function ), both terms are often used interchangeably
Ω of the current (see discussion of the polarization connect the oxidation and reducti
Energy Environ. Sci., 2009,2, 96-99
but MFC researchers
curve below), andshould canbebeaware 16 of the simply
described differences as in compounds (6).
 or concentration losses (see below).
In MFCs the measured cell voltage is usually a linear
V (35). In general, the difference between the measu
Power Curve / Polarization Curve
function of the current (see discussion of the polarization
voltage and the cell emf is referred to as overvoltag
curve below), and can be described simply as
the sum of the overpotentials of the anode and the c
and the ohmicE loss of the
) OCV - system
IR (12)
cell int

where IRint is the sumEcell

of ) internal
all emf - (Ση
EEMFC a +of
losses |Ση
the + IRΩwhich
c| MFC, )
good cathode
bad cathodeare proportional to the generated current (I) and internal
where
resistance of Ση
thea and
system
|Ση(R are
c| int the
). A overpotentials
comparison of eqs of11theand ano
12 shows
thethat the overpotentials
cathode respectively, of the
andanodeIRΩ isand thethe cathode
sum of al
that occur
losses under
which openarecircuit conditions
proportional toare
theincluded
generated in thecur
Mass Transfer/
Rin = value
Rext of OCV
and ohmic inresistance
eq 12, while of thethesystemcurrent
(RΩ). dependent
The overpo
overpotentials of the electrodes
of the electrodes are generally and current
ohmic lossesdependentof thean
systemMFCare they
captured in IRintbe
can roughly . MFC systemsasthat
categorized
loss
are well
follows: (i) ac
described
losses;by (ii)
eq bacterial
12 show slope
ametabolic
maximum
= RΩ
power
losses; andoutput whentr
(iii) mass
the internal resistance, Rint , is equal
assuming currenttodependent
external 
 resistance,
or concentration losses (see below).
Rext (52). Although Rint includes overpotential more than just ohmic
can be neglected
In MFCs the measured cell voltage is usually a
resistance (RΩ), both terms are often used interchangeably
Energy Environ. Sci., 2009,2, 96-99
but MFCfunction of theshould
researchers current be(see
aware discussion of the pola
of the differences in
curve
these two below),
terms. MFCand can be described
performance simplyinas
can be assessed terms
of both overpotentials 17 and ohmic losses or in terms of OCV
 Reduce Voltage Loss
• Ohmic loss
 Ohmic losses can be reduced by minimizing
loss due to the resistance to the flow of the electrode spacing, using a membrane with
electrons through the electrodes and a low resistivity, checking thoroughly all
interconnections, and to the flow of ions contacts, and (if practical) increasing solution
through membrane and the anodic and conductivity to the maximum tolerated by the
bacteria.
cathodic electrolytes
Low activation losses can be achieved by
• Activation Losses 
 increasing the electrode surface area,
Due to the activation energy needed for improving electrode catalysis, increasing the
an oxidation/reduction reaction operating temperature, and through the
establishment of an enriched biofilm on the
• Concentration Losses 
 electrode(s)
Concentration losses (or concentration Concentration losses occur mainly at high
polarization) occur when the rate of current densities due to limited mass transfer of
mass transport of a species to or from chemical species by diffusion to the electrode
surface. Enhance mixing or lower operation
the electrode limits current production
current density can help.
• Bacterial Metabolic Losses 
 The potential of the anode should be kept as
Bacteria can shift their metabolism and low (negative) as possible. However, if the
this determines if electron has higher anode potential becomes too low, electron
possibility to transfer outside cell or not. transport will be inhibited —>needs to be
further studied
18
To Be Continued…

19