Journal of Power Sources 261 (2014) 332e336
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Journal of Power Sources
journal homepage: www.elsevier.com/locate/jpowsour
Short communication
A membraneless single compartment abiotic glucose fuel cell
Gymama Slaughter*, Joshua Sunday
Bioelectronics Laboratory, Department of Computer Science and Electrical Engineering, University of Maryland Baltimore County, Baltimore,
MD 21250, United States
h i g h l i g h t s
Selectively catalyze glucose in the presence of oxygen in abiotic fuel cell.
Abiotic catalyst Al/Au/ZnO prepared using hydrothermal method.
Abiotic glucose fuel cell possesses an open-circuit voltage of 840 mV.
A maximum power density of 16.2 mW cm 2 at a cell voltage of 495 mV was obtained.
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 14 November 2013
Received in revised form
17 March 2014
Accepted 19 March 2014
Available online 27 March 2014
A simple energy harvesting strategy has been developed to selectively catalyze glucose in the presence of
oxygen in a glucose/O2 fuel cell. The anode consists of an abiotic catalyst Al/Au/ZnO, in which ZnO seed
layer was deposited on the surface of Al/Au substrate using hydrothermal method. The cathode is
constructed from a single rod of platinum with an outer diameter of 500 mm. The abiotic glucose fuel cell
was studied in phosphate buffer solution (pH 7.4) containing 5 mM glucose at a temperature of 22 C. The
cell is characterized according to its open-circuit voltage, polarization profile, and power density plot.
Under these conditions, the abiotic glucose fuel cell possesses an open-circuit voltage of 840 mV and
delivered a maximum power density of 16.2 mW cm 2 at a cell voltage of 495 mV. These characteristics
are comparable to biofuel cell utilizing a much more complex system design. Such low-cost lightweight
abiotic catalyzed glucose fuel cells have a great promise to be optimized, miniaturized to power bioimplantable devices.
Ó 2014 Elsevier B.V. All rights reserved.
Keywords:
Membraneless
Glucose fuel cell
Zinc oxide
Abiotic catalyst
1. Introduction
Bio-implantable devices, such as implantable glucose biosensors,
require a power source, which may be provided by charging of a
battery. The two basic and most immediate challenges facing bioimplantable devices include (1) a high desire that bio-implantable
devices are self-powered without using a battery and (2) the power source that can drive bio-implantable devices must not add
much weight to the bio-implantable device. Therefore, it is important
to exploit innovative nanotechnologies that harvest energy from the
environment for self-powering these bio-implantable devices. Selfpowering bio-implantable devices have an enormous potential to
improve individual’s well-being. A key advantage of self-powered
bio-implantable devices is that they usually operate at extremely
low power (nW to mW) [1]. As a result, the biochemical energy harvested from within the human body is sufficient to power these
* Corresponding author. Tel.: þ1 410 455 8483; fax: þ1 410 455 3969.
E-mail address: gslaught@umbc.edu (G. Slaughter).
http://dx.doi.org/10.1016/j.jpowsour.2014.03.090
0378-7753/Ó 2014 Elsevier B.V. All rights reserved.
systems. By harvesting a small fraction of this energy into electricity,
sufficient energy can be generated for self-powering wireless bioimplantable devices by harvesting energy directly from the biological fluid without using external battery sources. The realization of
glucose as an ideal fuel source for bio-implantable devices such as
miniaturized biosensors [2], microactuators [3], and pacemakers [4]
has received significant attention in the development and characterization of enzymatic biofuel cells which convert the biochemical
energy from glucose into electrical energy [5].
In enzymatic biofuel cells, glucose is oxidized at the anode by
glucose oxidase and oxygen is reduced at the cathode by laccase or
bilirubin oxidase [6]. In non-compartmentalized enzymatic biofuel
cells, the presence of oxygen and glucose mixture results in the
reduction at the cathode as well as at the anode, which results in a
decrease in the overall power output of such a device [7]. Moreover,
there are significant problems with extending the lifetime and
durability of these biocatalysts and hence further decreasing the
efficiency of enzymatic biofuel cells since these enzymes have
different optimum operating pH and temperature conditions and
may require the use of electron transfer mediators [8]. To overcome
G. Slaughter, J. Sunday / Journal of Power Sources 261 (2014) 332e336
these problems several approaches have been considered such as
the use of enzyme with reconstructed active centers that are less
sensitive to oxygen [9], inorganic materials such as osmium containing redox polymers [10,11] and carbon nanotubes [4,12e15]
that act as mediators or the combination of inorganic mediators
and biocatalyst [16] in order to facilitate the efficient electron
transfer between the anode and cathode. Glucose dehydrogenase is
frequently used in enzyme-biofuel cells and requires the immobilization of NADþ cofactor. The co-immobilization of NADþ cofactor
requires the utilization of complex procedures [17], which limits its
application in the bio-implantable devices [18]. Thus, in order to
achieve kinetically preferential electron transfer, O2 dependent and
NADþ dependent enzymatic biofuel cells must employ complex
multimolecular arrangement in the fabrication of the cells. These
multimolecular ensembles are not readily adaptable for batch
fabrication and are insufficient to provide the long-term power that
bio-implantable devices require. Although abiotic glucose fuel cells
exhibit higher stability and lifetime than enzymatic biofuel cells,
abiotic glucose fuel cells have received very little attention for being
used as a potential power source for bio-implantable devices.
Generally, abiotic glucose fuel cell are used to convert the chemical
energy of glucose and oxygen in biological fluid into electricity
using noble metal as the catalyst to abiotically catalyzed glucose
because they are inert and biocompatible [19]. In this contribution,
we refocus the attention on the development of a simple approach
to harvest the excellent electrochemical properties of the Al, Au,
and ZnO by combining them via sputtering and hydrothermal
methods to fabricate an abiotic glucose/oxygen fuel cell. We utilized the Al/Au/ZnO as the anode and platinum as the cathode
material to selectively catalyze glucose oxidation and oxygen
reduction in the presence of oxygen.
333
Fig. 1. Cross-section process flow diagram of the fabrication process used in the design
of the Al/Au/ZnO anode.
Pure Aluminum foil (99.9999%, 250 mm thick) was purchased
from Alfa Aesar. Zinc chloride (99.99%), triethenamine (TEA,
99.99%), and all chemical reagents were purchased from Sigmae
Aldrich and all supplementary chemicals were of analytical grades
and used without further purification. All solutions were prepared
with 18.2 MU cm Milli-Q water.
natural solvent evaporation to form a thick layer of seeds. Between
coatings, the substrate was annealed at 150 C for 1 h to ensure
nanoparticles adhesion to the substrate surface. The dip-coating
and annealing process was repeated until a thick, uniform seed
layer was obtained on the surface of the electrode. Subsequently,
the Al/Au/ZnO substrates were repeatedly rinsed using deionized
water to remove unbound salt and dried at 30 C in a convection
oven overnight. The cathode for oxygen reduction was achieved by
utilizing platinum rod (f ¼ 500 mm) since platinum has been show
to exhibit the highest oxygen reduction potential when compared
to palladium, gold and silver in phosphate buffer pH ¼ 7 [21]. The
morphology and structural characteristics of the as-fabricated,
annealed Al/Au/ZnO were observed by means of scanning electron microscopy (JEOL JSM-5600 SEM).
2.2. Fabrication
2.3. Experimental setup
2.2.1. Al/Au/ZnO anode fabrication and Pt cathode
Fig. 1 illustrates the anode fabrication steps for glucose oxidation. Briefly, rectangular (6 mm 5 mm) strips of pure Al foils were
used as substrates and were cleaned to remove contaminants by
standard cleanroom procedures prior to use. Thin layers of gold
(40 nm) were sputtered onto the surface of the aluminum substrate
using the magnetron sputtering process. ZnO seed layers were
coated on the Al/Au sputtered substrate by a simple solegel process
[20] under mild conditions. The ZnO precursors were prepared
using zinc chloride and propanol. Briefly, the reaction solution for
ZnO seed layer fabrication was prepared by mixing appropriate
quantities of propanol and 0.4 M zinc chloride solution under
constant stirring at 75 C. Equimolar of triethenamine was added
dropwise to stabilized the precursor solution and produce a final
0.1 M homogeneous ZnO nanosol. The ZnO nanosol was covered
and maintained under constant stirring at 85 C until a homogeneous solution was observed. The reaction mixture was aged at
room temperature until the desired consistency was obtained. The
Al/Au/ZnO seed layers were established by coating the Al/Au substrate with the ZnO nanosol using dip-coating method followed by
2.3.1. Glucose fuel cell setup and measurements
The abiotic glucose fuel cell was built using the as-fabricated Al/
Au/ZnO as the anode and a platinum rod as the cathode positioned
20 mm apart in the cell. Fig. 2 shows the schematic diagram of the
experiment setup. All experiments were performed at physiological
glucose and pH levels (5.0 mM glucose in 0.1 M phosphate buffer
solution (pH ¼ 7.4)) at 22 C. The Al/Au/ZnO selectively catalyzes
glucose oxidation in the presence of oxygen and the highly specific
platinum catalyzes oxygen reduction reaction at the cathode,
thereby enabling the use of a membraneless single compartment
design for testing. The currentevoltage outputs of the cell were
obtained under various loads with 5 mM glucose in phosphate
buffer. The load was connected directly in parallel with the glucose
fuel cell. Fluke 87V True RMS multimeter was used to capture the
glucose fuel cell voltage and current readings.
2. Experimental methods
2.1. Materials
3. Results and discussion
Recently, zinc oxide nanostructures have received significant
attention in the construction of sensors [22] and piezoelectric
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G. Slaughter, J. Sunday / Journal of Power Sources 261 (2014) 332e336
Fig. 2. Experimental set-up for the glucose fuel cell characterization.
Fig. 4. Cyclic voltammograms (CVs) of the Al/Au/ZnO electrode in air-saturated
phosphate buffer solution (pH 7.4) without glucose, with 5 mM, 10 mM, and 25 mM
glucose. Scan rate; 20 mV s 1.
generators [23]; however their potential has yet to be explored for
abiotic glucose fuel cell applications. Therefore, ZnO seed layers
were prepared via solegel and dip-coating techniques, and the Al/
Au/ZnO substrate was examined by SEM. Fig. 3 shows the SEM
images of the as-fabricated Al/Au/ZnO substrate before and after
dip-coating with ZnO nanosol. The representative morphology
confirms that before dip-coating of ZnO seed layers, the Al/Au
substrate was observed to have homogeneous surfaces, whereas
after dip-coating in the ZnO nanosol and annealing at 150 C
resulted in nanostructured surface. The nanostructures adopted an
irregular morphology with different sized particles (nm range) and
formed agglomerates due to the synthesis condition of depositing
ZnO seed layers on the surface of Al/Au substrate.
Fig. 4 depicts the cyclic voltammograms (CVs) of the Al/Au/ZnO
electrode measured in air-saturated phosphate buffer solution
without glucose (purple curve (in the web version)), with 5 mM
glucose (blue curve), 10 mM glucose (red curve) and 25 mM glucose
(green), respectively. The addition of glucose resulted in the formation of greater oxidation currents. The electrochemical oxidation/reduction of ZnO resulted in redox peaks with anodic and
cathodic peak potentials of 1.60 V and 0.51 V in phosphate buffer
solution (purple curve). This electrochemical reaction of ZnO appears to be irreversible since the half-wave potential is 1.05 V and
the limiting oxidation current is 677.5 mA. It has been reported that
the electrochemical redox reaction of ZnO structures in batteries is
not reversible [24]. The peak potentials and peak currents of the
redox reaction of the ZnO nanostructures with and without glucose
were very similar. The expected reduction of water was not
observed in the CV possibly due to the electrocatalytic activity of
ZnO. However, the anodic current produced by the Al/Au/ZnO
electrode in the presence of glucose corresponds to glucose
oxidation at potentials more positive than 338 mV vs Ag/AgCl,
while the cathodic current for the oxygen reduction was observed
at 445 mV vs Ag/AgCl, thus allowing potential difference of ca.
107 mV between the anodic and cathodic reactions. The increase in
oxidation currents corresponds with the glucose oxidation under
ZnO electrocatalysis.
The working principle of the abiotic glucose fuel cell is based on
the electrochemical property of the Al/Au/ZnOePt to oxidize
glucose in the presence of oxygen to gluconic acid and reduce oxygen to water, thereby resulting in the generation of electrons
(Scheme 1a). In addition, the electrons in the valence band of ZnO
acts as charge carriers causing ZnO to exhibit n-type conductivity.
Hence, the Zinc in ZnO is acts as a deep acceptor, whereas oxygen
acts as a deep donor. In the present experiment, ZnO nanostructures can electronically mediate the glucose oxidation indicating that the Al/Au/ZnO had good catalytic performance. During
the electrochemical reaction, the relatively dilute potassium
phosphate is reacting with ZnO by donating its electrons present in
its phosphate group to zinc in ZnO. The interaction between these
two materials is given Scheme 1b. The generated electrons flow
from the anode to the cathode through the external load circuit.
This flow of electron process results in a d.c. power source. The
highest theoretical voltage that may be obtained from abiotic
glucose fuel cell is dictated by thermodynamics and is 1.3 V [21].
Fig. 3. SEM micrograph of the hydrothermally deposited ZnO nanoparticles on Al/Au.
Insert: SEM image of the Al/Au.
Scheme 1. Schematic illustration of glucose oxidation mechanism of Al/Au/ZnO
electrodes.
G. Slaughter, J. Sunday / Journal of Power Sources 261 (2014) 332e336
Fig. 5. Currentevoltage polarization curve of the glucose fuel cell at different external
loads in air-saturated phosphate buffer (pH 7.4) containing 5 mM glucose.
Fig. 5 shows the current voltage behavior of the glucose fuel cell at
different external loads in 5 mM glucose in phosphate buffer solution saturated with air. 5 mM glucose in buffered solution (pH 7.4)
was chosen because blood glucose concentration fluctuates between 4 and 6 mM and has a pH of 7.35e7.45 [11]. The open circuit
voltage and short circuit current of the fuel cell was 880 mV and
28 mA, respectively. In addition, the Al/Au/ZnO fuel cell operates
without the use of a membrane/stack material to spatially separate
the electrodes within a single compartment containing glucose and
oxygen. This characteristic is especially unique with respect to
abiotic fuel cells as most operate using a membrane in order to
isolate the anode and cathode during fuel cell operation. However,
the lower open circuit potential observed is due to the occurrence
of mixed potentials at both anode and cathode as a result of small
amount of glucose and oxygen reacting at the same electrode,
which is consistent with abiotic fuel cells [25]. The Al/Au/ZnO
shows high degree of selectively oxidizing glucose in the presence
of oxygen. To obtain this theoretical voltage, optimization of various
factors is required. However, the most important factor is the
electrocatalytic surface interactions. The output of the Al/Au/ZnOe
Pt fuel could be improved by growing a homogenous layer of ZnO
on the Al/Au substrate in the future, so that higher electrocatalytic
335
Fig. 7. Voltage generated by cell operated on a 54 kU resistance as a function of time.
surface area can be realized in order to obtain a greater voltage
from the catalysis of glucose [26]. The power of the cell at different
loads is shown in Fig. 6. The power density of the Al/Au/ZnOePt fuel
cell depends on load matching and was found to have a maximum
at 54 kU with a corresponding power density of 16.2 mW cm 2 and
a current density of 111.1 mA cm 2, which is substantially higher
than reported values for a stacked electrode, enzyme-free glucose
fuel cell [27] and PQQ-dependent glucose dehydrogenase biofuel
cell [15]. In addition, multiple Al/Au/ZnOePt fuel cells could
potentially be connected in series and/or parallel to further boost
the power output.
Fig. 7 shows the stability curve of cell operating continuously
under 54 kU load in air-saturated 5 mM glucose. The cell demonstrated stable electrical power output over a long period of time (ca.
9 h) followed by a gradual decay in activity, thus confirming the
stability of the abiotic catalyst systems. In comparison to enzymatic
glucose biofuel cells, one of the major limitations is the performance deteriorate over time as a result of enzymes degradation
[28], which renders their application in a long-term bio-implantable device difficult as seen in the case of glucose oxidase and
glucose dehydrogenase based fuel cells [7,15]. Therefore, the Al/Au/
ZnOePt fuel cell which harvests the biochemical energy of glucose
is an attractive alternative to enzymatic glucose biofuel cells for its
increased power output and lifetime. The reported fuel cell has the
benefit of high power density and potentially operating over longer
time periods because the lifetime is only limited by the degradation
of the device, which with the advancement in technology can be
engineered to be durable.
4. Conclusion
Fig. 6. Power versus current density at different loads of the Al/Au/ZnOePt glucose
fuel cell. Insert: Power generated on a variable-load resistance.
Developing innovative nanotechnologies that harvest energy
from our personal environment for self-powering bio-implantable
devices is highly desirable for long-term bio-implantable devices.
Herein, an Al/Au/ZnO abiotic catalyst was fabricated by hydrothermal and dip-coating techniques for the development of an
abiotically catalyzed glucose fuel cell that may enable selfpowering of bio-implantable devices. The characterization of the
Al/Au/ZnO anode was revealed by the formation of ZnO nanostructures on the surface of the Al/Au substrate having excellent
glucose catalysis capability. The Al/Au/ZnOePt glucose fuel cell was
demonstrated to harvest the biochemical energy from glucose in
the presence of oxygen. A peak power density of 16.2 mW cm 2 and
a current density of 111.1 mA cm 2 was obtained. This is an
improvement over the current abiotic fuel cell technology that
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G. Slaughter, J. Sunday / Journal of Power Sources 261 (2014) 332e336
utilizes membrane/stack design scheme to achieve glucose and
oxygen separation by decreasing the occurrence of the oxidation of
glucose and reduction of oxygen at the same electrode. Thus, the
present contribution provides a platform to use Al/Au/ZnO nanostructured electrode to formulate an efficient membraneless single
compartment abiotic glucose fuel cell with stable electrical power
over a long period of time. The fabricated abiotic fuel cell could be
broadly exploited with more wide application for self-powering
bio-implantable devices. Future work will involve chromatographic analysis of the species in solution to confirm the reaction
products, reaction mechanism and the limiting reagents, if any.
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