Environmental Technology

ISSN: 0959-3330 (Print) 1479-487X (Online) Journal homepage: https://www.tandfonline.com/loi/tent20

Synthesis of nickel-based layered double

hydroxide (LDH) and their adsorption on carbon
felt fibres: application as low cost cathode catalyst
in microbial fuel cell (MFC)

Meriem Djellali, Mostefa Kameche, Hakima Kebaili, Mohamed Mustapha

Bouhent & Abdellah Benhamou

To cite this article: Meriem Djellali, Mostefa Kameche, Hakima Kebaili, Mohamed Mustapha
Bouhent & Abdellah Benhamou (2019): Synthesis of nickel-based layered double hydroxide (LDH)
and their adsorption on carbon felt fibres: application as low cost cathode catalyst in microbial fuel
cell (MFC), Environmental Technology, DOI: 10.1080/09593330.2019.1635652

To link to this article: https://doi.org/10.1080/09593330.2019.1635652

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Published online: 16 Jul 2019.

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ENVIRONMENTAL TECHNOLOGY
https://doi.org/10.1080/09593330.2019.1635652

Synthesis of nickel-based layered double hydroxide (LDH) and their adsorption on

carbon felt fibres: application as low cost cathode catalyst in microbial fuel cell
(MFC)
Meriem Djellali a,b, Mostefa Kamechea,b, Hakima Kebailia,b, Mohamed Mustapha Bouhenta,b and
Abdellah Benhamoua,c
a
Université des Sciences et de la Technologie d’Oran Mohamed-Boudiaf, Oran, Algérie; bLaboratoire d’Ingénierie des Procédés de
l’Environnement, Université des Sciences et de la Technologie d’Oran Mohamed-Boudiaf, Oran, Algérie; cFaculté de chimie, Laboratoire de
Physico-Chimie des Matériaux, Catalyse et Environnement, Université des Sciences et de la Technologie d’Oran Mohamed-Boudiaf, Oran,
Algérie

ABSTRACT ARTICLE HISTORY

Following their successful utilization as novel bioanodes in Microbial Fuel Cells (MFCs), Layered Received 13 October 2018
Double Hydroxide (LDH) were tested in the present investigation, as promising cathodes to Accepted 16 June 2019
reduce electrons coming from oxidation of organic matter in the anode compartment, in the
KEYWORDS
presence of oxygen used as successful oxidant. Therefore, the LDH samples Ni3Al-LDH with the Nickel-Aluminium layered
ionic ratio Ni2+/Al3+ equal to 3, were synthesized and added by adsorption to Carbon Felt (CF) double hydroxide synthesis;
fibres. They were then stored separately in three electrolyte solutions KCl, NiCl2 and AlCl3 used carbon cathode catalyst;
as catholytes in the MFCs. Effects of the active cationic sites located inside the Ni3Al-LDH on microbial fuel cell; fruit waste
these electrolytes, were discussed in terms of energies produced by these MFCs. The structure treatment; low cost energy
and morphology of the synthesized LDH, were studied by using the analytical techniques XRD,
FTIRS and SEM, while the electrode performances of the LDH-electrodes were investigated with
the electrochemical methods CV and EIS. It was revealed that the CF modified with Ni3Al-LDH
cathode and conditioned in the NiCl2 electrolyte solution yielded the highest energy harvesting
for the MFC (i.e. 3.2 µW/cm2). This power density output was similar to previous clean one-
compartment MFC. However, it was less expensive than an Enzymatic Fuel Cell (45 µW/cm2),
making in evidence the highest cost of the material. Thus, by taking into account these
encouraging findings, the low cost materials used in MFCs held great promise for practical
application in electrochemical power devices and therefore fruit waste treatment.

Abbreviations: ACFC: Air Cathode Fuel Cell; ADEFC: Alkaline Direct Ethanol Fuel Cell; AFC: Alcaline
Fuel Cell; BET: Brunauer–Emmett–Teller; BFC: Biological Fuel Cell; CF: Carbon Felt; CV: Cyclic
Voltammetry; DGFC: Direct Glucose Fuel Cell; DMFC: Direct Methanol Fuel Cell; EFC: Enzymatic
Fuel Cell; EIS: Electrochemical Impedance Spectroscopy; FC: Fuel Cell; FTIR: Fourier Transform
Infra Red spectroscopy; LDH: Layered Double Hydroxide; MEC: Microbial Electrolysis Cell; MFC:
Microbial Fuel Cell; Mg-Al-CO23 -LDH: Layered Double Hydroxide Magnesium-Aluminium-
Carbonate; Ni-Al-LDH: Layered Double Hydroxide Nickel-Aluminium; OCP: Open Circuit Potential;
SEM: Scanning Electron Microscope; TG/DTA: ThermoGravimetric and Differential Thermal
Analysis; XRD: X-Ray Diffraction.

CONTACT Meriem Djellali meriem.djellali@univ-usto.dz; meriemdjellali@gmail.com Université des Sciences et de la Technologie d’Oran-Mohamed
Boudiaf, USTO-MB, BP 1505, El M’naouar, 31000 Oran, Algérie
© 2019 Informa UK Limited, trading as Taylor & Francis Group
2 M. DJELLALI ET AL.
1. Introduction
LDHs are known as hydrotalcite-like clays with the
chemical composition formula of [MII1–xMIII x+ n−
x (OH)2] [Ax/n
x− II III
yH2O] , where M and M represent divalent and triva-
lent metal ions within the brucite-like layers and An−
interlayer anions [1,2]. LDHs are therefore class of ionic
solids characterized by a layered structure having
generic layer sequences. They can be readily synthesized
under laboratory conditions with easily controllable
chemical composition of the layer and interlayer
domains [3].
Nowadays, LDHs intercalates are attracting much
attention and having novel advanced applications in
medicine and agriculture [4,5]. For example, some drug
molecules may be intercalated; the resulting nanocom-
posites have potential use in controlled release systems
[6,7], reducing the frequency of medication doses
needed for treatment. Furthermore, agrochemical inter-
calates are of interest because of the potential utilization
of LDHs to remove agrochemicals from polluted water,
reducing the likelihood of eutrophication [8]. Also,
using Mg-Al layered double hydroxide to eliminate the
pollutants as heavy metal from aqueous solutions [9].
The composition of LDHs could provide a positively
charged environment to interchange organic molecules
[10], such as carboxylic acids [11], anionic polymers
[12], cyclodextrin [13], organic phosphoric acids [14]
and fullerene [15]. Such modified electrodes have also
been used effectively to detect phenol [16] and uric
acid [17]. Removal of hazardous fluoride from drinking
water by using layered double hydroxide/cellulose com-
posite [18].
MFC was revealed as one of recent methods of renew-
able energy recuperation, the direct conversion of
organic matter to electricity by using bacteria [19]. The
efficiency of modified cathodes by oxides was also
confirmed in the MFCs [20]. With the aimtobe used asva-
luable choice for DGFC application, modified grapheme
LDH nanocomposites were synthetized as advanced
electrode for glucose electro oxidation [21]. In separate
studies, platinum and nickel nanoparticles were success-
fully electro-deposited on glassy carbon electrode for
glucose electro-oxidation to be used in AFCs [22]. Plati-
num nanoparticles were also supported on reduced gra-
phene oxideas potential catalyst for the improvement of
electro oxidation of methanol to be used in DMFC [23].
On energy scale, enzymes encapsulated within sol–
gel matrices have been also used for BFC applications
[24]. In effect, LDHs Zn2Cr–ABTS and Zn2Al–Fe(CN)6
LDH, have been already synthesized to confirm the inter-
calation of redox anions between inorganic layers, to be
used as electrical connection in the EFC. Thus, with a two
compartment configuration using LDH, a maximum
power density of 45 µW.cm−2 was obtained [25].
Indeed, novel grapheme modified polymers were elabo-
rated for EFCs operating in plant leaves [26]. Electroche-
mical activities in MFC, were studied by electro-
deposition of manganese dioxide on polypyrrole-
coated stainless steel [27]. Also, electrochemical study
of buffered ferric chloride was carried out elsewhere as
terminal electron acceptor in two-compartment MFC
[28]. Based on these interesting properties and appli-
cations, LDHs should be potentially attractive materials
as electrode surface modifications. Besides, LDHs have
been used as electrolyte in ADEFC [29]. For more electro-
chemical applications, LDHs were successfully utilized as
sensors, electrocatalysts and super capacitors [30,31]. In
FC applications, Ni-Al-LDH was used as catalytic promo-
ter to the electrolyte membrane/electrocatalyst interface
[32]. Furthermore, the anionic clays Mg-Al-CO23 -LDH and
Ni-Al-Cl-LDH were also used as cathode catalyst layers for
the conception of more favourable AFCs [33].
Indeed, LDHs containing Ni and Al as electrode
modifiers can be adsorbed on carbon-felt fibres for the
improvement of oxygen reduction capacity at cathode
in MFC and may be used successfully as previously
[21]. In addition, LDH materials have several advantages,
such as their low cost, environment-friendly, versatility of
their chemical composition, unique anion exchange,
intercalation properties and chemical stability. On the
other hand, their use in particular energy research pro-
duces some challenging physical and chemical aspects
that need to be addressed. In particular, Ni-Al-LDH and
carbon materials composites have been investigated
intensively as promising capacitive materials due to
high redox activity enhanced electrochemical
performances.
In view of the above-mentioned interesting electroca-
talytic properties of these materials, we found it is useful
to make a further investigation towards the integration
of these novel materials in MFC. In this biological
energy device, we used microorganisms (bacteria) as bio-
catalyst to prove the feasibility of the process in depollut-
ing wastewater though producing low bio-energy. The
metabolic pathways of microorganisms related to the
production of electricity in MFC, are anaerobic digestion,
anaerobic respiration and fermentation. During the
anaerobic respiration of microorganisms, the electrons
are diverted from their respiratory chain to a final accep-
tor. Microorganisms utilize nitrates, sulfates, CO2, metal
ions or organic acids as final electron acceptors. Fermen-
tation is also a metabolic pathway for which organic
compounds are oxidized.
Rabaey & Verstraete et al. [34] have already estab-
lished the link between anode potential and microbial

metabolism. As soon as the MFC starts working, the
potential of the anode is high and therefore its voltage
is low. The high potential of the anode selects thus the
microorganisms. As they are being developed, the
speed of their metabolism simultaneously increases the
production of the current, and the potential of the
anode begins to decrease.
In order to be effective, a MFC must use a fuel (sub-
strate) of the lowest equilibrium potential coupled with
an oxidant of the highest potential. For example, a BFC
using the oxidation of acetate at the anode would consti-
tute an alternative not far in power, from the oxidation of
hydrogen. The standard potential of the CO2 / acetate
redox couple (i.e. −0.28 V) is comparable to that of H+/
H2 (i.e. −0.42 V).
The present work investigates thus the synthesis of
Ni3Al-Cl-LDH with molar metal ratio equal to 3 (Ni2+/Al3
+ diffractometer working at 40 kV and 30 mA and
) in order to decrease the layer density charge of LDH
and therefore to increase the amount of the transition
metal (nickel). The synthesized Ni3Al-Cl-LDH, was used
as a novel catalyst in MFC. Its crystallographic and mor-
phological features were examined using conventional
analytical techniques XRD, FTIR, TG/DTA, FE-SEM. Fur-
thermore, its electrochemical properties were also evalu-
ated with CV and EIS. Moreover, in contrast to Kubo et al.
2012 [35] who used a two-chamber AFC with an anion
exchange membrane as separator and LDH-modified
electrodes, we expose in this study a successful appli-
cation of our newly elaborated LDH in a two compart-
ment MFC using a cation exchange membrane as
separator between catholyte and anolyte chambers. Sat-
isfactorily on energy scale, the power density delivered
by our MFC was quite similar to the one-compartment
FC [36] but very much different from that obtained
with the two-compartment AFC [37].
2. Experimental set up
2.1. Reagents
The Salts solutions were prepared from analytical
grade reagents: AlCl3.6H2O (>98%, Sigma), NiCl2.6H2O
(99%, Sigma), NaOH (98%, Fluka), HCl (37%, Fluka).
All preparations were done with de-ionized water
(18.2 MOhm.cm).
2.2. Synthesis and elaboration of Ni3-Al-Cl LDH
The material containing nickel and aluminium (LDH-
Ni3Al), was synthesized by co-precipitation method.
The salt solutions of NiCl2.6H2O and AlCl3.9H2O respect-
ively with the molar proportion 3 were therefore pre-
pared. Then, they were added drop-wise into 100 ml
ENVIRONMENTAL TECHNOLOGY 3
of de-carbonized water, in which the precipitation-pH
was maintained constant at a value of 8.5 with a sol-
ution of NaOH (1.0 M). Further addition was completed
after 6 h and then left for 24 h under N2 flow. The
resulting suspension was washed several times with
de-carbonized water and finally dried inside oven at
60° [38].
In order to make evidence the existence of the
LDH phase, the composition and the morphology of
the obtained material were characterized by conven-
tional analytical techniques (XRD, FTIR, TG/DTA, FE-SEM,
SEM)
2.3. Characterization of synthesized Ni3-Al-LDH
XRD data were collected in a BRUKER D8-ADVANCE
using Ni-filtred Cu-Kα radiation, scanning from 2° to
75° in 2θ degrees. FTIR spectra were recorded with
spectrometer BRUKER IFS 66V-S and NICOLET-20SXC.
Each sample was placed in the sample holder as KBr
pellets (2% wt sample concentration pelletized at
10 ton) and scanned from 4000 to 400 cm−1 with
2 cm−1 resolution. The specific total surface area was
obtained by applying BET method. The thermal
behaviour of the prepared materials, was analyzed
from the simultaneously recorded TG and DTA curve
in SEIKO SSC/5200 equipment. Measurements were
carried out under air atmosphere (flow of 100 mL/
min) from room temperature to 1000°C at 10°C/min
heating rate. The microscopic analyses of surface of
Ni3Al-LDH sample were done with FE-SEM equipment
FEI-NOVANANOSEM 230. The preparations were per-
formed by adhering particle samples on a carbon
tape with FE-SEM a gold conductive coating on the
surface, using Philips XL30S-FEG. On the other hand,
images of the pristine CF and the modified cathode
CF-Ni3Al-LDH have been realized using JSM-6610LA
SEM.
2.4. Preparation of LDH-based cathode for MFC
LDH modified cathode was prepared by solvent casting
procedure according to a method described previously
[39]. In effect, a sample of pristine CF of area 14.88 cm2,
was washed with hydrochloride acid (0.1 M) to remove
all organic matter. As suggested by Pérez-Ramirez et al.
[40], the amount of 1.0 mg/mL Ni-Al- LDH aqueous sus-
pension was dispersed overnight under stirring in dis-
tilled water. Then, the cleaned CF was immersed into
the suspension for 24 h and finally was allowed to dry
in air.
4 M. DJELLALI ET AL.

2.5. MFC design

The MFC consisted of two half-glass cells separated by
the cation exchange membrane (Nafion117) and CF elec-
trodes. One-half of the cell contained pristine CF as
anode and leachate of fruit wastes for the formation of
electroactive bio-film. The oxidation of the organic
matter in particular sodium acetate, generated electrons
and protons.
The electrons travelled alongside the external circuit,
whereas the protons diffused across the membrane.
The other half of the cell contained the LDH modified
CF as cathode and an electrolyte solution (KCl or NiCl2
or ALCl3) which received the electrons coming from
the external circuit. Besides, dissolved oxygen in the
Figure 1. Xray diffractogram of Ni3Al-LDH.
catholyte helped and enhanced the reduction of
protons to yield water molecules. The circuit of the FC
was closed with an outside resistance of 1000 Ω. At the 3. Results
beginning, the voltage of the cell varied owing to acclim-
3.1. Structural and morphological
ation of the electrode to medium and then became more
characterization of LDH
stable giving more significant current values. In general,
MFC became mature and reached the highest voltage The XRD patterns of prepared Ni3Al-LDH are shown in
values after being operated during a week. Figure 1. The diffraction pattern exhibited the character-
istic reflections (003), (006) and (110), corresponding to
2.6. Electrochemical measurements hexagonal LDH crystal structure that was crystallized
with well-ordered structures. More intensive and
Electrochemical characterization was evaluated with CV
sharper reflections of the (003) and (006) planes at low
conducted by a potentiostat-galvanostat Voltalab
2q angles values (11°–23°) were observed. The average
PGZ301 in a three-electrode setup electrochemical cell.
(d) basal spacing d003 (Table 1) of Ni3-AL-LDH was
Platinum wire was used as auxiliary electrode, Ag/AgCl
around 0.78 nm and consistent with the presence of
as reference electrode and Ni-Al-LDH modified CF as
chloride intercalated anion. The cell parameters (c) and
working electrode. CV was carried out using the potential
(a) of the Rhombohedral structure were determined
range +1000 mV to −1000 mV at scan rates 5, 10, 20, 50
from the positions of the (003), (006) and (110) diffraction
and 100 mV/s. The EIS experiment was also performed in
lines, respectively. The lattice parameter a = 2d (110) cor-
the frequency range 10 kHz–100 MHz under the appli-
responded to an average cation–cation distance calcu-
cation of perturbation super imposed voltage of 10 mV,
lated from the (110) reflection, while the c parameter
using the same apparatus.
attributed to three times the thickness of d003 par-
Unlike CV, in EIS the potentiostat-galvanostat does
ameter. In this case, c was calculated from two diffraction
not impose a linear but a sinusoidal signal at the
lines using the equation [2]
working electrode around a fixed potential (in general
OCP). Therefore, three parameters should be considered 3
c = [d(003) + 2d(006)] (1)
to make the measurements: the OCP, the amplitude of 2
the perturbation signal potential and the frequency Determined lattice parameters (c) and (a) are listed in
range studied. In our case, the impedance spectra were Table 1.
recorded by applying the perturbation potential signal Figure 2 illustrates the FTIR analyses of synthesized
amplitude 21.23 mV (i.e. 10% OCP 212.3 mV), and the fre- Ni3Al-LDH, usually used to indicate the functional and
quency range varying from 10 kHz to 100 mHz. Exper-
imentally, when EIS measurements were set on the
potentiostat, the value of the OCP was shown automati- Table 1. Unit cell parameters for the hydrotalcite-derived
materials, calculated from their respective XRD patterns.
cally on the screen along with its corresponding horizon-
Lattice
tal line (sometimes fluctuating a little bit) during a very parameters
short time. Then the spectrum started to be plotted Sample name d (003) nm d (006) nm d (110) nm (nm)
after having set the value of the perturbation potential Ni3-Al-LDH 0.783 0.392 0.15043 c A
2.56 0.30
(i.e. 21 mV) and not that of OCP.

Figure 2. FT-IR of Ni3Al-LDH.
chemical bonds present in a compound. The broad peak
around 3496 cm−1 is attributed to the stretching of OH−
groups attached to metal ions. The bending vibration of
interlayer water was found, at around 1633 cm−1. The
lower wave number bands at 400–1000 cm−1 were due
to LDH lattice vibrations (M-O, O-M-O) [41]. The band
557 cm−1 could be assigned to M-O, stretching modes
at 1363 cm−1 and associated with the symmetric
vibration of the anionic carbonate function of interlayer
Cl− anions, showing that there was a slight
Figure 3. FE-SEM images of Ni3Al-LDH.
ENVIRONMENTAL TECHNOLOGY 5
contamination between Cl− and interlayer H2O through
the strong hydrogen bonding.
On the other hand, the morphology of Ni3Al-LDH was
investigated by SEM (Figure 3). Aggregates of small par-
ticles have been identified for the sample Ni3Al-LDH. The
hexagonal shape characteristic for co-precipitated LDH,
was identified in our prepared samples. However, it
was rather difficult to estimate the actual particle size
of our samples from our micrographs due to a high
agglomeration of LDH [42] using the sample of the CF
washed with HCl 0.1N. The randomly arranged cylindrical
fibres with a smooth surface, were observed. In addition,
for the cathode CF modified with NiAl-LDH, it was also
possible to observe the particles of the clear deposition
of anionic clays on the fibres of CF.
The TG and DTA curves are presented in Figure 4. Con-
tinuous weight loss was observed in the TG plots up to
114°C, as previously evidenced by Lansink Rotgerink
et al. [38]. The physically absorbed water, was usually
removed around 100°C, a shoulder being observed
around 100°C. The DTA profile showed two endothermic
peaks, one at 268°C and the second between 114 and
403°C, depending on sample composition. Generally,
for a LDH structure, the endothermic peak that occurs
at lowest temperature (usually 110–200°C) could be
attributed to the loss of interlayer water [2]. The
second endothermic peak may be related to the
decomposition of the brucite like layer along with the
6 M. DJELLALI ET AL.

Figure 4. TG/ATD curve of Ni3Al-LDH. Figure 5. Current density-Time curves of MFCs.

loss of interlayer anions. More specifically, the cationic biofilms to form and to expand. Contrary, the potassium
layers dehydroxylate and the interlayer lost weight MFC did not give practically any voltage. As soon as the
usually in the temperature at around 403°C. MFCs started to function, they registered the value 0.01 V
On the other hand, The BET analysis reveals that the and rose steeply to values ranging from 0.05 to 0.07 V,
specific surface area of the Ni3Al-LDH was 22.34 g/m2 where they remained almost constant during the first
coherent with the considering composition ratio of 10 h. This performance corresponded in general to a
LDH particles, as previously mentioned by [2]. pattern of growth owing to the basic adaptation of the
microorganisms to the growing conditions before start-
ing the exponential growth. After 30 h of functioning, a
3.2. MFC performance small quantity of sodium acetate (60 mM) was added
to the anolyte compartment, to motivate the bacterial
3.2.1. Evolution curves
growth. As a result, the voltage of the nickel MFC
According to Logan et al. [43] and Cercado Quezeda [44],
jumped up to 0.14 V, while that of aluminium MFC
the oxidation of acetate, electron donor (R.1) and the
increased a little bit because the quantity of Aluminium
reduction of oxygen, electron acceptor (R.2) take place
is less than that of Nickel in composition of LDH (ration
at the anode and the cathode respectively. Their corre-
Ni2+/Al3+ = 3). Then, the voltage dropped off to initial
sponding:
value 0.06 V as a result of sodium acetate depletion,
CH3 COO− + 4H2 O  2HCO− +
3 + 9H + 8e
−
(R.1) which was kept constant during 110 h of working.
Then, the voltages decreased very slowly until the end
2H+ + 2e− + 12O2  H2 O (R.2)
of the experiment after 170 h (i.e. 7 days).
The equilibrium potentials of the anode (Ea) and the
cathode (Ec) can be obtained using Nernst’s law: 3.2.2. Coulomb efficiency (CE)

 When the MFC was operating, electrons coming out from
RT (CH3 COO− )
Ea = Ea − ln
0
(2) the oxidation of organic matter at the bio-anode in the
8F [HCO− + 9
3 ][H ] presence of the electroactive bio-film, arrived through
  the external circuit at the cathode where they were com-
RT 1
EC = EC0 − ln (3) bined with protons and dissolved oxygen to yield dro-
PO2 [H+ ]
4F 4
plets of water in the catholyte; the Ni-LDH catalyst
The difference between these two potentials, gives the increased and improved the speed of the reaction. As
theoretical electromotive force of the MFC i.e. the OCP cited in literature, by using nickel as catalyst in the
(the discharge resistance is infinity). However, by using cathode (carbon paper) of MEC, the production of the
the discharge resistance 1000 Ω, the data of voltage gas hydrogen was increased drastically from 0.02 to
were obtained. Figure 5 illustrates thus the evolution vol- 4.14 L.j−1 [45]. It is thus clear that nickel is a very good
tages of the three MFCs with the different catholytes catalyst for the reduction of proton to gas hydrogen.
NiCl2, AlCl3 and KCl. The voltages of nickel and aluminum As we mentioned before, neither the cathode potential
MFCs increased right up after an initial lag phase that nor the anode were measured separately, during the
corresponded to the time required for electroactive experiment. However, they were connected between
 ENVIRONMENTAL TECHNOLOGY 7

Figure 6. Experimental current yield of MFC with NiCl2-CF-NiAl-

LDH modified cathode. Figure 7. Coulomb efficiency of MFC using Ni3AL-LDH/CF in
three different catholytes.

them via the external resistance, and the voltage was

et al., [46] (43.50%) who used very expensive pure strain
therefore recorded.
of bacteria (Saccharomyces cerevisiae) asbiocatalyst and
In order to evaluateCE of MFC i.e. the fraction of elec-
methylene blue as mediator [47].
trons extracted for conversion into electricity,the curve
current density versus time was plotted (Figure 6). The
integral given by Equation (4a), yields the experimental
3.2.3. Polarization and power density curves
electron charge density represented by the area
As shown in Figure 8, the polarization curve exhibits
located between the curve and initial and final times.
three distinct regions. In effect, due to the activation
Then CE unit representative of electron loss within
resulting from the energy loss during the initiation of
MFC, was calculated using Equation (5). It represents
the Ox/Red reactions and electron transfer between
the percentage of electrons recovered from the organic
the bacterial cell and the anodic surface, the MFC
matter Qexp versus the theoretical maximum number of
began by creating a short-circuit current density at the
electrons Qth (Equation 4b) involved in the oxidation
highest voltage (0.06 V). Then, it displayed an Ohmic
reaction [46].
linear drop caused by the electrolyte. At last, it gave
t
the maximum open-circuit current density (0.19 A/m2)
Qexp = idt (4a) owing to the loss of concentration taking place during
0
the diffusion phenomenon. This finding is in good agree-
nFCV
Qth = (4b) ment with previous results obtained by Zerrouki [48]
M using a two-compartment MFC.
Qexp
CE = ∗100 (5)
Qth
where (i) was current over time expressed in seconds, (n)
number of moles of electrons produced per mole of
acetate (n = 8), (F ) Faraday 96,500 C.mol−1, (C ) consumed
substrate concentration (C = 60 mM), V analyte volume
(V = 70 mL). The calculated Qexp during the working
time of the MFC with NiCl2 as catholyte was 1.59 C/cm2.
Figure 7 shows the bar chart of yield of CE of the MFC
calculated with Equation (5) using the three electrolyte
solutions KCl, NiCl2 and AlCl3. It is clear that the MFC
with NiCl2 is the highest confirming that the MFC with
modified carbon felt fibres with Ni3Al-LDH and NiCl2 as
catholyte has the maximum CE due to the presence of
Nickel like the transition metal (20.62%). However, this
value is relatively lower than that obtained by Mardiana Figure 8. Polarization curve of MFC with catholyte NiCl2.
8 M. DJELLALI ET AL.
Figure 9. Power density curves of MFCs with different catholytes.
The power density was at last determined in terms of
current density by varying the external resistance from
10 MΩ down to 100 Ω. Generally, the value of the
current stabilized within 3 min. However, the required
time needed to reach the initial value, depended on
the value of the resistance. In effect, the smaller the
value of the resistance, the higher is the cell discharge.
When the MFC was connected to the external resistance
(Rext), the voltage cell (V) and the current (I) were fixed by
the load. Thus, the MFC performance was determined by
the output power that was evaluated using Equation (6).
In order to compare electrical performance of different
systems, the output power was normalized to anode
surface area. More specifically, with the goal to
compare the performance of the anode, the power
density (µW/cm2) was calculated using the area of the
anode.
P = U.I
The power curves are represented in Figure 9. They
illustrate the maximum energy delivered by the three
MFCs. As expected by the previous research, the power
density improved with increasing values of current
density and got optimal values. Effectively, the
maximum explicit powers delivered by the NiCl2/MFC
were 3.2 µW/cm2. However the AlCl3/MFC power
Table 2. Maximum power density delivered by our MFC and compared to some LDH fuel cells.
LDH composition Fuel cell type
Ni3Al-Cl Two-compartment MFC Cation exchange membrane
Mg2-Al –Cl One-compartment MFC
Zn2-Al –Cl
Zn2Cr–ABTS Two-compartment
Enzymatic fuel cell
Mg2-Al –CO23 Two-compartment AFC Anion exchange membrane
Ni2Al CO23
density was less important (i.e. 0.6 µW/cm2) but quite
similar to the KCl/MFC (0.5 µW/cm2).
The power output of our MFC is 3.2 μW/cm2 i.e.
32 mW/m2, which is in the same order of magnitude as
others functionning similarly and using O2 as oxidant
at cathode, pigsty effluent (45 mW/m2) [49]; sediment
(38 mW/m2) [50]; aneorobic sludge (48 mW/m2) [51].
The MFC technology uses le biocatalyseur (i.e. microor-
ganisms) which adhere to the electrode and act as an
electro-catalyst. Microorganisms have the ability to
exchange electrons with the material of an electrode
using the proper reactions of their metabolism; they
are electrochemically active » or « electroactive. They
can come from a pure culture, a mixed culture or a
natural consortium. Although they produce lower
energy, they reduce the pollution by transforming
organic wastes into energy. In contrast, alkaline, hydro-
gen and direct methanol fuel cells utilize platinum
(very expensive) as catalyst. However, their power
outputs are relatively higher.
Table 2 summarizes the values of power density
obtained with our MFC and compared to others using
other LDH materials and cell configurations that have
been reported [25,35,36]. The power density of our
MFC with two compartments with cationic exchange
membrane used NiCl2 catholyte and Ni3Al-LDH
modified carbon felt fibres was rather comparable
(3.2 µW/cm2) to that of Djebbi et al. [36] using one
chamber fuel cell (3 or 4 µW/cm2). However, the value
of the power density of the enzymatic MFC was much
greater (45 µW/cm2) due to the intercalated enzyme
inside the LDH interlayer space. And finally, with the
AFC used by Kubo et al. [35] the highest power density
was obtained (40,000 µW/cm2) owing to alkaline
medium. The enzymatic transesterification has attracted
(6) much attention for biodiesel production as it produces
high purity product and enables easy separation from
the by-product, glycerol. But the cost of enzyme
remains a barrier for its industrial implementation. In
order to increase the cost effectiveness of the process,
the enzyme (both intracellular and extracellular) is re-
used by immobilizing in a suitable biomass support par-
ticle and that has resulted in considerable increase in
efficiency. On the other hand, exist the AFCs operate
Membrane type Power density (µW/cm2) Reference
3.2 This work
4 Djebbi et al. [36]
3
45 Zebda et al. [25]
40,000 Kubo et al. [37]
52,000
 ENVIRONMENTAL TECHNOLOGY 9

between ambient temperature and 90°C with an electri- 3.3. Electrochemical characterization
cal efficiency higher than FCs with acidic electrolyte. The
3.3.1. Cyclic voltammetry
operating temperature normally is about 80°C the main
CV measurement was carried out using Voltalab 40 PGZ
difficulties with this FC type are: (1) carbon monoxide,
301 potentiostat-Galvanostat controlled by personal
always found in hydrogen produced by reforming
computer via Votamaster version 4 software. The electro-
hydrocarbon or alcohol fuels, is a poison to the pre-
chemical experiments were carried out in electrolyte sol-
cious metal electrocatalysts, and (2) carbon dioxide
utions KCl, NiCl2 and AlCl3 separately, inside a three-
(in either fuel or air) will react with the KOH electrolyte
electrode glass cell composed of reference electrode
to form potassium carbonate. As such, applications are
(Ag/AgCl), counter electrode (platinum wire, 1 cm long)
essentially limited to those where either pure oxygen
and working electrode (Carbon Felt-based electrode).
or hydrogen can be used. mostly because of the
CV voltammograms were obtained at different scan
high sensitivity of their performance on the presence
rates (5, 10, 20, 50 and 100 mV/s) using the window-
of carbon [47].
potential −1000, +1000 mV/s versus AgCl. This range
In BFCs, catalysis is provided by bio-elements: redox
should be large enough to include the oxidation–
enzymes for EFCs, or microorganisms (bacteria, algae,
reduction values of electroactive analytes as well as the
yeasts …) for MFCs. Enzymes are commercial and some-
open circuit voltage of the MFC.
times expensive, while bacteria and algae are abundant
Figure 10 shows the typical CV voltammogram
in nature. In EFC, two catalysts are used: an enzyme at
obtained with the three electrolyte solutions. The
the anode for the oxidation of fuel (glucose) and
current rose when the voltage reached the analyte
another enzyme at the cathode for the reduction of
reduction potential in the forward scan and then
oxygen. While in the MFC, the electroactive biofilm (con-
dropped off as the concentration of the analyte was
sorsium of microorganisms) is used as a biocatalyst for
lowered around the surface of the electrode. Then,
the oxidation of the polluting organic matter and a
when the applied potential was inverted, it re-oxidized
carbon support for the reduction of the dissolved
the product formed in the first reduction reaction, and
oxygen. The power delivered by the glucose/oxygen
produced the oxidation current of reversed polarity
EFC (19 μW/cm2 at 0.23 [52] is greater than that of our
during the backward scan. It can be seen that the peaks
MFC 3 μW/cm2).
displayed on the voltammogram in the forward sweep,
EFCs have been the subject of much work in recent
corresponded to pure reduction of K+, Ni2+ and Al3+
years. They constitute an alternative device of FC for
cations on electrode and within LDH skeleton. Really,
the production of electricity. Even if the powers delivered
the highest currents were recorded with Ni2+ and Al3+
remain very low (of the order of a few tens of micro-
cations being initially present within the LDH. Neverthe-
watts), the possibilities of application as a source of
less, the voltammogram of the LDH electrode obtained
energy for micro-machines, micro-sensors, show the rel-
in KCl solution gave relatively lower broad peak.
evance of these systems. While MFCs deliver lower
In general, for ideal electroactive species the oxidation
powers but they clean up the space invaded by house-
peak was similar to the reduction peak. However, by
hold and other wastes. They can therefore be exploitable
for the depollution, for example a pleasure garden
invaded with wastewater. The conversion of polluted
water into electrical energy serves for lighting this
garden.
Previous studies carried out by Zebda et al. [25],
Djebbi et al. [36] and Kubo et al. [37], showed that the
LDH improved greatly the power outputs of AFC and
EFC. In the present investigation, the output of our
MFC has also been improved using CF modified by
Ni3Al-HDL. We think that this newly elaborated catalyst
may be regarded as a useful material for practical appli-
cations in MFCs, especially in the treatment of waste-
water and food industry effluents. In CV, as shown in
Figure 10 for a given scan rate the oxidation peak
takes place at negative value of voltage close to the stan-
dard RedOx potential of nickel (i.e. −0.25 V), confirming Figure 10. Cyclic voltammogram curve of NiCl2/Ni3Al- LDH/
its oxidation. carbon felt cathode at scan rates (5-10-20-50-100 mV/s).
10 M. DJELLALI ET AL.
using the modified LDH-electrode in NiCl2 electrolyte sol-
ution, the reduction was the main reaction since the
highest peak appeared at a potential close to the theor-
etical oxydo-reduction potential of couple Ni2+/Ni (i.e.
−0.25 V) and on the other it was not far enough from
that of the open-circuit potential of the MFC (i.e.
∼−0.20 V). However, the peak located at about +0.60 V
could be attributed perhaps to the oxydo-reduction of
other electroactive species. In contrast, during the back-
ward sweep, visibly there was no oxidation detected
compared to composition MgAl-LDH/FC and ACFC like
design of MFC (+ 0.150 V) as found by Djebbi et al.
[36]. We may attribute this fact to the non-reversibility
of the CF electrode modified with LDH. The voltage of
oxidation peaks ranged from −0.160 V to −0.102 V in
scan rate interval (5–50 mV/s), making in evidence that
oxidation is taking place for negative values of voltage
(with two oxidation peaks given by Voltamaster software
at 10 mV/s; 8.6 mA/cm2/−0.114 V and 14.0 mA/cm2/
+0.672 V).
Besides, CV made it possible to know the type of
regime in which the system was performed. Indeed,
the current profile of an electro-active biofilm was
similar to a theoretical sigmoid characteristic of a station-
ary regime as shown in the above-mentioned
Figure 11. Current density versus voltage scan rate, using electrolytes KCl, NiCl2 and AlCl3.
voltamogramm. However, under transient conditions,
the dependence between the current peak of nickel oxi-
dation value and the potential sweep rate gave access to
the material transfer characteristics between the cathode
(CF-Ni3AlLDH) and a given solution. Two phenomena
occurred: the reduction current varied linearly with the
square root of voltage scan rate i.e. Ipeak (Red) = I (√ʋ).
This phenomenon applied for KCl catholyte suggesting
the mater transfer to be limited by the diffusion of the
species in solution. However, when the reduction
current varied linearly with the voltage scan rate i.e.
Ipeak (Red) = I (ʋ). This case applied successfully for cath-
olytes NiCl2 and AlCl3 suggesting a surface controlled
process, in qualitative good agreement with previous
work using LDH-electrode in one-compartment fuel cell
[37]. Thus, the effect of the chemical composition
inside LDH in particular the presence of Ni2+ cations,
was well evidenced by CV (Figure 11).
In effect, the potential difference between the anode
and cathode (i.e. voltage of the fuel cell) was measured
versus time during the course of all experiments
carried out, using a load resistance. Nevertheless, in
order to obtain more information on the functioning of
the fuel cell, it is possible to follow the potential differ-
ence between the anode or cathode and a reference
 ENVIRONMENTAL TECHNOLOGY 11

electrode (Ag/AgCl). As it is suggested by the reviewer

this procedure may be beneficial and would perhaps
provide an idea on values of redox potentials of the reac-
tions taking place in both anode and cathode chambers.
Unfortunately, it was not followed by us; the values of
redox peaks were recorded separately using another CV.
In our MFC, at the cathode there was a reduction of
the dissolved oxygen. The presence of adsorbed nickel
(as nanoparticles catalyst) on the carbon felt enhanced
the reaction by allowing a relatively greater voltage
output. Obviously, the oxidation peak appearing in CV
voltammogram, is attributed to nickel cation present
inside the LDH.
Once the carbon felt was enriched with nickel catalyst,
it was immersed in its corresponding electrolyte solution Figure 12. Nyquist plots obtained for carbon felt catholyte
(i.e. NiCl2) used as catholyte. The CV characterization modified Ni-Al-LDH materials using electrolytes KCl, NiCl2 and
proves that the nickel present inside the LDH, was AlCl3.
reduced to Ni0 and then re-oxidized yielding new Ni2+.
As long as the catalyst was present inside the LDH, the
Table 3. Values of double layer capacitance (C ), electrolyte
MFC delivered a voltage. This procedure took, in
resistance (Re), charge transfer resistance (RCT) and of cathode
general more than three weeks. using the three catholytes of MFCs (KCl, NiCl2 and AlCl3).
Impedance component KCl NiCl2 AlCl3
3.3.2. Impedance spectroscopy C (mF/cm2) 15.99 26.56 142.1
To better understand the influence of adding Ni3Al LDH Re (µΩ/cm2) 42.56 12.09 11.59
RCT (µΩ/cm2) 31.44 29.95 28.2
in the present reduction processes, a series of EIS
measurements were also performed with modified CF
cathode using three samples of catholytes at applied
and the good electrochemical performance of syn-
potential for frequencies ranging from 10 kHz to
thesized LDH in all catholytes. The electrolyte resistances
100 mHz and under open circuit conditions. The above-
(i.e. Re) using NiCl2 and AlCl3 were similar to each other
mentioned apparatus was used and gave experimental
12.09 and 11.56 µΩ/cm2 but completely different from
spectra data which were plotted according to Nyquist
that of KCl catholyte (42.56 µΩ/cm2). This difference
diagram. They were then analyzed with Randles equival-
was due perhaps to the fact that LDH contained
ent electrical circuit (C, Re, RCT) [53], where C was the
cations Ni2+ and Al3+ which decreased the values of
capacitance of the double layer, Re the electrolyte resist-
the electrolyte resistance.
ance and RCT the charge transfer resistance.
In general, the impedance response evidenced a
In general, the impedance spectra of the Nyquist plot
decrease that can be reflected by drastic increase in
had two distinct parts (I) and (II). Part (I) was a semi-circu-
the LDH electronic conductivity, as progressive intercala-
lar arc at the low-frequency attributed to the charge-
tion of metal cations took place. This finding was in quali-
transfer resistance (RCT) in parallel to the double layer
tative good agreement with that reported by Kubo et al.
capacitance (C ). Whilst part (II) was a quasi-straight line
[37], as the immobilization of the Ni3Al-LDH nano-sheets
at high frequency attributed to electrolyte resistance
on the FC fibres, increased its conductivity.
(Re) in series to the parallel circuit (RCT, C ). As shown in
Figure 12, the calculated values of capacitance were
15.99, 26.56 and 142.1 (mF/cm2) for the modified
4. Conclusion
carbon felt cathode with Ni3Al-LDH in catholytes KCl,
NiCl2, AlCl3 respectively, are listed in Table 3. Further- In the present investigation, it was shown that the LDH
more, once CF cathode modified with LDH nanolayers could be adsorbed on CF fibres to elaborate cathodes
was conditioned in the AlCl3 solution, it led to a higher suitable for the reduction of electrons coming from oxi-
surface area and improved as result the electric dation of organic matter in a MFC. Ni-Al LDH composites
double-layer capacitance due to electron charge are expected to be applied as high rate discharge
density using trivalent aluminium cations, as has been cathode materials in the next generation batteries.
already noticed elsewhere [54]. However, the calculated They were acted therefore as reduction active material
values of Rct confirmed the non-blocking properties for energy conversion. Moreover, the power
12 M. DJELLALI ET AL.
performance of our MFC obtained with NiCl2 as catholyte
was promising since it was quite similar to that obtained
previously by other workers using one-compartment fuel
and Mg and Zn-LDH as anodes. Satisfactorily on energy
scale, the power density delivered by our MFC was
quite similar to the one-compartment fuel cell [36] but
very much different from that obtained with the two-
compartment AFC [35]. Further improvement could cer-
tainly be expected by using simultaneously the LDH with
CF fibres as anode and cathode for a MFC.
Acknowledgements
The authors are grateful to Dr. T. Sahraoui for technical assist-
ance of SEM analysis in laboratory LMESM at USTO-MB.
Disclosure statement
No potential conflict of interest was reported by the authors.
ORCID
Meriem Djellali http://orcid.org/0000-0003-0505-7164
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