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Ionics (2015) 21:26032607

DOI 10.1007/s11581-015-1434-y

ORIGINAL PAPER

Studies on noble metal-free carbon-based cathodes


for magnesiumhydrogen peroxide fuel cells
K. Naga Mahesh 1 & R. Balaji 1 & K. S. Dhathathreyan 1

Received: 21 November 2014 / Revised: 17 March 2015 / Accepted: 29 March 2015 / Published online: 12 April 2015
# Springer-Verlag Berlin Heidelberg 2015

Abstract The magnesiumhydrogen peroxide (MgH2O2)


fuel cell is developed using a noble metal-free carbon-based
cathode. Carbon felt and carbon cloth are used as a cathode,
and the performance was evaluated in a single cell of 30 cm2
electrode area with aq. NaCl as an anolyte and acidified hydrogen peroxide solution as a catholyte. The influence of hydrogen peroxide, sulfuric acid concentration, operating temperature, and flow rate on the performance of MgH2O2 fuel
cell is studied. Compared with carbon cloth-based cathode, a
carbon felt-based cathode has shown better fuel cell performance. The maximum power density of 91 mW cm2 is obtained with carbon felt-based cathode, and the stability of the
MgH2O2 is tested for about 24 h.
Keywords MgH2O2 fuel cell . Carbon felt . Carbon cloth .
Hydrogen peroxide

Introduction
The development of high energy density and environmentfriendly power sources for undersea application is essential
due to an increase in interest to utilize abundant marine resources, like biological, gas, and oil. Aluminum and magnesium metals have gained attention to use as anode materials
for power source in undersea applications. This is because of
their low atomic weight, high faradic capacity, standard electrode potential, and easy-to-use seawater as an electrolyte
[15]. Electrochemical systems based on magnesiumhydrogen peroxide (MgH2O2) fuel cells have high energy density
and can produce electricity by converting its stored chemical
energy [6, 7]. The MgH2O2 fuel cell has a theoretical voltage
of 4.14 V, and the corresponding half-cell and overall reaction
are as follows [5]:

Anode : MgMg2 2e E0 2:37 VvsSHE


Cathode : H2 O2 2H 2e 2H2 O E0 1:77 Vvs:SHE
Overallreaction : Mg H2 O2 2H Mg2 2H2 O E cell 4:14 Vvs:SHE

The performance and stability of the MgH2O2 fuel cell are


principally dependent on the cathode materials used in the
cell. Many attempts have been made on cathode materials

* R. Balaji
rbalaji@arci.res.in
1

Centre for Fuel Cell Technology, International Advanced Research


Centre for Powder Metallurgy and New Materials (ARCI) , IITM
Research Park, Taramani, Chennai 600113, Tamil Nadu, India

1
2
3

especially on the development of catalyst for hydrogen peroxide reduction reaction [79]. Besette et al. [10] studied the use
of microfiber carbon electrode (MCE) covered by Pd/Ir as a
cathode in AlH2O2 fuel cells and obtained a maximum power density of 90 mW cm2 with Pd/Ir loading of 10 mg cm2.
Shu et al. [7] studied palladium-coated titanium foam cathodes for the MgH2O2 fuel cell, and the performance was
evaluated at different operating conditions. Further, they have
also studied the Mg-air fuel cell performance using a carbon
fiber felt cathode. Yang et al. [8] used nickel foam-supported
Pd/Ag as a cathode in the MgH2O2 fuel cell and achieved a
power density of 138 mW cm2 at 50 C.

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Thus, most of the studies are based on the development of highly active electrocatalyst for hydrogen peroxide reaction. To achieve better and stable fuel cell
performance, the material properties of cathode substrate
need to be considered. For optimized performance substrates with suitable porosity, high surface area, high
electrical conductivity, and high electrochemical activity
toward the reactions between redox species may be
used. Considering the above aspects, materials like
graphite and carbon in the form of porous structure
can be good electrode materials. These forms of materials are widely used in fuel cells and flow battery to
achieve optimized performance [11]. Hence, in this
study, an attempt has been made to use carbon felt
and carbon cloth as a cathode in the MgH2O2 fuel cell,
and its performance was studied with different operating
parameters.

Experimental
Materials
All chemicals (reagent grade) were obtained from M/s.
SRL Chemicals, India, and were used as received. Deionized water was used for all the experiments. The
anode was an AZ61 magnesium alloy supplied by
M/s. Omega Enterprises, India. The conductive carbon
fiber cloth (AvCarb 40) was procured from M/s. Ballard
Materials Products, USA, and the carbon felt of 4 mm
thick was procured from M/s. Nickunj Eximp (P) Ltd.,
India.

Fig. 1 Schematic representation


of the MgH2O2 fuel cell

Ionics (2015) 21:26032607

MgH2O2 single-cell assembly and performance


evaluation
The performance studies for carbon cloth and carbon felt as
cathodes were evaluated in the homemade MgH2O2 fuel cell
of 30-cm2 area single-cell assembly, and Fig. 1 shows the
schematic representation of the MgH2O2 fuel cell. The electrode area was 5.5 cm5.5 cm. Nafion 117 membrane was
placed in between two graphite blocks, an AZ61 magnesium
anode was introduced in between two graphite blocks with
straight parallel groves at the center, and the whole single cell
setup was clamped together using nuts and bolts. The cell had
suitable inlet/outlet for circulating solution for both sides of
anode and cathode and have provision for operating at various
set temperatures. The distance between the membrane and
electrodes is 1 mm for the MgAZ61 anode as well as for
the cathode (carbon felt and carbon cloth). The testing of the
cell was carried out by circulating different concentrations of
hydrogen peroxide and sulfuric acid at the cathode and 0.6 M
sodium chloride solution at the anode using a peristaltic pump.
The IV characteristics of the cell were measured using an
electronic load bank (model 6314A; Chroma ATE Inc.,
Taiwan).
Electrochemical studies
The cathodic polarization behavior of carbon electrode and
chronoamperometry (CA) studies for Mg anode were carried
out using electrochemical work station (Solartron 1470E) in a
three-electrode cell assembly with saturated calomel electrode
(SCE) as a reference electrode and platinum wire as a counter
electrode. The polarization was performed in acidified hydrogen peroxide solution from 0 to 1.2 V at a scan rate of

Ionics (2015) 21:26032607

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5 mV s1 at room temperature. CA studies were carried out


using MgAZ61 of 3.3-cm2 area as a working electrode, the
electrolyte was 0.68 M NaCl solution, and the experiment was
performed at 60 C and at voltages of 1.35 V.

Results and discussion


Influence of carbon
The performance of the MgH2O2 fuel cell using carbon cloth
and carbon felt as a cathode at 70 C is shown in Fig. 2. It is
observed that the carbon felt-based cathode has shown higher
open circuit potential (OCP) than that of carbon cloth-based
cathode. It can also be seen from Fig. 2 that the carbon felt
cathode has shown a maximum power density of
91 mW cm2, whereas the carbon cloth cathode has shown a
maximum power density of 9 mW cm2, which is lower compared to carbon felt under same operating conditions. It may
be attributed to high surface area, high electrical conductivity,
high porosity, and large pores formed by interlace fibers,
allowing the electrolyte to flow through the felts, which facilitates the reactants transport and reduce the cell resistance [12,
13]. The cathodic polarization studies of carbon electrode in
2.0 M H2O2 +2.0 M H2SO4 solution are shown in Fig. 3. The
observed current density is more for carbon felt than carbon
cloth-based cathode. Thus, it may be concluded that the better
performance of the carbon felt-based cell is due to its better
polarization characteristics.

Fig. 3 Cathodic polarization of carbon cloth and carbon felt cathodes in


2.0 M H2O2 +2.0 M H2SO4 solution; scan rate, 5 mV s1

shown in Fig. 4. It can be seen that with an increase in cell


temperatures from 35 to 70 C, the cell performance was improved by an increase in cell voltage from 0.86 to 1.41 V at a
current density of 60 mA cm2 and a maximum power density
of 91 mW cm2 obtained at 70 C. It may be attributed to
improved reaction kinetics of anodic dissolution of magnesium and electro-reduction of hydrogen peroxide. The slight
voltage instability observed in the mass transport region at
higher current densities may be attributed to the formation of
more gas bubbles due to the decomposition of hydrogen peroxide during discharge process [7].

Effect of temperature

Effect of hydrogen peroxide and sulfuric acid


concentrations

The influence of operating cell temperature on the performance of the MgH2O2 fuel cell is studied at various operating temperatures ranging from 35 to 70 C, and the results are

The influence of hydrogen peroxide concentration on the performance of the fuel cell has been investigated by varying the
concentrations of H2O2 from 0.2 to 2.0 M, and the sulfuric

Fig. 2 Comparison of carbon cloth and carbon felt at an operating


temperature of 70 C with current and power densities. Anolyte, 0.6 M
NaCl; catholyte, 2.0 M H2O2 +2.0 M H2SO4; flow rate, 50 ml min1.
cathode, carbon cloth and carbon felt; anode, MgAZ61 alloy

Fig. 4 Performance of the MgH2O2 cell at 35, 40, 50, 60, and 70 C;
anolyte, 0.6 M NaCl; catholyte, 2.0 M H2O2 +2.0 M H2SO4; flow rate,
50 ml min1; cathode, carbon felt; anode, MgAZ61 alloy

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Ionics (2015) 21:26032607

Fig. 5 Effect of H2O2 concentration at constant 2.0 M H2SO4 at a flow


rate of 50 ml min1 at 60 C. Anolyte, 0.6 M NaCl; cathode, carbon felt;
anode, MgAZ61 alloy

Fig. 7 Performance of carbon felt cathode at flow rates of 20, 50, and
100 ml min1 at 70 C. Anolyte, 0.6 M NaCl; catholyte, 2.0 M H2O2 +
2.0 M H2SO4; cathode, carbon felt; anode, MgAZ61 alloy

acid concentration was kept constant at 2.0 M. The results of


these experiments are shown in Fig. 5. With an increase in
hydrogen peroxide concentration, the cell performance improved. It may be attributed to increased decomposition rate
of hydrogen peroxide at higher concentration and enhancement of the reduction reaction kinetics [7]. From Fig. 5, it
can be seen that the fluctuation in mass transport region is
due to the possible decomposition of hydrogen peroxide and
production of gas bubbles that, in turn, hinders the mass transfer of the reactants [7].
Further, the influence of sulfuric acid concentration was
studied, keeping the concentration of hydrogen peroxide constant at 2.0 M. The performance of the fuel cell increases by
increasing the sulfuric acid concentration of 0.2 to 2.0 M, and
further increase in concentration did not show any significant
improvement in the performance (Fig. 6). As expressed in
Eq. (2), the electrochemical reaction of hydrogen peroxide

involves H+ as a reactant. The formation of H+ in solution is


less at lower sulfuric acid concentrations, which facilitates
chemical decomposition of hydrogen peroxide rather than
electrochemical reduction, resulting in worst fuel cell
performance.

Fig. 6 Effect of H2SO4 concentration at constant 2.0 M H2O2 at a flow


rate of 50 ml min1 at 60 C. Anolyte, 0.6 M NaCl; cathode, carbon felt;
anode, MgAZ61 alloy

Effect of flow rate


The influence of reactant flow rate was studied, and the results
were shown in Fig. 7. The anolyte and catholyte flow rates
were varied simultaneously from 20 to 100 ml min1 at 70 C.
The fuel cell performed better with an increase in flow rate
from 20 to 50 ml min1, and further increase in flow rate did
not show any significant gain in the performance. Hence, the
optimum flow rate was fixed to 50 ml min1.

Fig. 8 Chronoamperometry studies for the MgAZ61 anode. The


voltage applied was 1.35 V (vs. SCE) at a temperature of 60 C

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MgH2O2 fuel cell with carbon felt-based cathode was operated steadily for about 26 h under a given current density of
50 mA cm2.
Acknowledgments The authors would like to thank Dr. G.
Sundararajan, Director, ARCI, for his constant support and encouragement and the Department of Science and Technology, Government of
India, for financial assistance.

References
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Fig. 9 Performance of carbon felt cathode under constant current density
of 50 mA cm2 at a flow rate of 50 ml min1 at 60 C. Anolyte, 0.6 M
NaCl; catholyte, 2.0 M H2O2 +2.0 M H2SO4; cathode, carbon felt; anode,
MgAZ61 alloy

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Endurance study of MgH2O2 fuel cell


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anode, and it was replaced in regular interval.

Conclusion
In the present work, noble metal-free carbon-based cathode
was used in a MgH2O2 fuel cell. The MgH2O2 fuel cell with
carbon felt-based cathode shows a maximum power density of
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