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 Journal of Power Sources 275 (2015) 831e834

Contents lists available at ScienceDirect

Journal of Power Sources

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

A low-cost, high-performance zincehydrogen peroxide fuel cell

L. An, T.S. Zhao*, X.L. Zhou, X.H. Yan, C.Y. Jung
Department of Mechanical and Aerospace Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR,
China

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

A catalyst-free, high-performance Zn
eH2O2 fuel cell is proposed.
It consists of a redox flow cell with
redox ions regenerated by fuel/
oxidant.
It exhibits a peak power density of
1192 mW cm!2 at 60 " C.
The performance is much higher than
conventional cells with the same
fuel/oxidant.

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

Article history: Electric vehicles (EVs) are primarily limited by the distance they can travel, charge time and cost. Here we
Received 18 September 2014 report a catalyst-free, high-performance zincehydrogen peroxide fuel cell that consists of a redox flow
Received in revised form cell with the respective redox couple at the anode (V(II)/V(III)) and cathode (V(IV)/V(V)) regenerated by
13 November 2014
the fuel (zinc) and the oxidant (hydrogen peroxide). Unlike batteries that have low capacities and need to
Accepted 14 November 2014
Available online 15 November 2014
be frequently charged, the present fuel cell enables future vehicles to travel farther distances on one
charge and almost instantaneous charge time. More importantly, it is demonstrated that this novel fuel
cell exhibits an extraordinarily high peak power density of 1192 mW cm!2 at 60 " C, a performance which
Keywords:
Fuel cell
is about five times higher than that of state-of-the-art conventional fuel cells of the kind (265 mW cm!2).
Zinc fueled fuel cell Another striking feature of the present fuel cell is that it does not require catalysts, allowing the power
Redox couple pack to be both cost-effective and durable. These important features make the present fuel cell a
Catalyst-free promising post lithium-ion technology, opening a sustainable way to propel next-generation vehicles.
Regeneration © 2014 Elsevier B.V. All rights reserved.
Power density

1. Introduction
Replacing petroleum with electric propulsion has been recog-
nized as an effective means to decrease the strain on the environ-
ment [1]. Lithium-ion technology currently dominates the battery
market of electric vehicles (EVs), but EVs have achieved little
market penetration, primarily because of the high cost and low
energy density of even state-of-the-art lithium-ion batteries [2]. An
alternative energy-conversion technology, fuel cells, which convert
* Corresponding author.
E-mail address: metzhao@ust.hk (T.S. Zhao).
chemical energy stored in a fuel directly into electrical energy, are
expected to become a key enabling technology for powering EVs,
due to its high energy density and comparatively short refueling
time [3,4].
Fuel cells, which power EVs, typically use hydrogen as a fuel.
This raises the issues of hydrogen production, transportation and
storage, all while minimizing cost. Moreover, commercialization of
hydrogen fueled fuel cells cannot be successfully achieved until
safety issues resulting from the use of pressurized hydrogen are
resolved, not to mention the high cost involved in the use of plat-
inum catalysts required for electrochemical reactions [5,6].

http://dx.doi.org/10.1016/j.jpowsour.2014.11.076
0378-7753/© 2014 Elsevier B.V. All rights reserved.
832 L. An et al. / Journal of Power Sources 275 (2015) 831e834
Alternative sources of fuel, such as zinc, have recently attracted
increasing attention. Fuel cells which use zinc as fuel not only
exhibit high energy density, but are also low in cost in comparison
to hydrogen fueled cells, since only non-precious metal catalysts
are required [7]. Zinc fueled fuel cells have, therefore, been recog-
nized as a promising power source to propel EVs. Unfortunately,
current state-of-the-art performance (265 mW cm 2) of zinc-
fueled fuel cells has not yet been able to meet requirements for
practical applications in EVs [2].
In this work, we propose a catalyst-free, high-performance
zincehydrogen peroxide fuel cell. This type of fuel cell consists of a
redox flow cell with the respective redox couple at the anode and
cathode regenerated by the fuel (zinc) and the oxidant (hydrogen
peroxide), as shown in Fig. 1. The introduction of two redox couples
to the conventional fuel cell system brings several striking features.
First, the absence of catalysts makes the present fuel cell cost-
effective. Second, the presence of redox couples significantly im-
proves the electrochemical kinetics, thereby resulting in a high-
performance fuel cell (1192 mW cm 2 at 60 ! C). Finally, the sole
use of carbon materials in preparing the electrodes makes this fuel
cell durable.
2. Working principle
Fig. 1 illustrates the working principle of the present fuel cell
system. Two redox couples, V(II)/V(III) and V(IV)/V(V), are used at
the anode and the cathode, respectively. At the anode, the redox
ions (V2þ) are oxidized by withdrawing electrons with the
following ionic equation [8]:
V2þ /V3þ þ e Ea0 ¼ 0:26V vs: SHE
Released electrons pass through an external electrical load and
arrive at the cathode. Protons migrate through the proton exchange
membrane from the anode to the cathode. At the cathode, redox
ions (VOþ 2 ) are reduced by receiving the released electrons [8]:
2þ
VOþ þ
2 þ 2H þ e /VO þ H2 O Ec0 ¼ 1:00V vs: SHE
3þ 2þ
The discharge products, V ions at the anode and VO ions at
the cathode, will be chemically charged (regenerated) by zinc and
hydrogen peroxide in respective reactors according to:
Reactor #1 : V3þ þ 1 2 Zn/V2þ þ 1 2Zn2þ
= =
Fig. 1. Schematic of the zincehydrogen peroxide fuel cell system.
Reactor #2 : VO2þ þ 1 2 H2 O2 /VOþ
=
2 þH
þ
(4)
The combination of Eqs. (1)e(4) results in an overall reaction of
this type of fuel cell:
Zn þ 2Hþ þ H2 O2 /Zn2þ þ 2H2 O (5)
3. Fuel-cell setup
In addition to a flow cell consisting of a membrane electrode
assembly (MEA) sandwiched between two flow fields, the present
fuel cell also includes two reactors for chemical charge, as shown in
Fig. 1. The MEA, with an active area of 1.0 cm $ 1.0 cm, was
comprised of an as-received Nafion 212 membrane between an
anode and a cathode [9]. Both the anode and cathode were made of
three pieces of carbon paper (SGL: 10 AA) [10]. The two reactors are
made of glass. The aqueous solutions containing 1.0 M vanadium
ions (vanadium sulfate: ZhongTian Chemical Ltd., China) and 2.5 M
sulfuric acid (SigmaeAldrich) were fed to the flow cell by using a 2-
channel peristaltic pump (WT-600-2J, Longerpump, China). The
cell temperature was measured with a thermocouple located at the
anode current collector, and two electrical heating rods were
installed in the fixtures to control the operating temperature [11].
Polarization curves were measured by an electric load (Arbin
BT2000) [12]. Potentiometric titration was conducted to examine
the chemical charges of V(III) ions by zinc (Aldrich) and V(IV) ions
by H2O2 (Honeywell), respectively. The potentials were measured
by a voltmeter with a Pt mesh as working electrode and a saturated
calomel electrode as reference electrode.
(1)
4. Results and discussion
4.1. Chemical charge
Fig. 2 shows the chemical charge processes of the vanadium ions
by zinc and hydrogen peroxide, respectively. It can be seen from
(2) Fig. 2a that adding zinc powder into the aqueous solution, initially
containing 1.0 M V(V) ions, changes the potential from 0.972 V
to 0.460 V, meaning that zinc can successively reduce the V(V)
ions to V(IV), V(III), finally V(II) ions. The potential change roughly
from 0.0 V to 0.3 V indicates that the discharge products at the
anode, V(III) ions, can be chemically charged to V(II) ions by zinc
(3) [13]. Similarly, it is seen from Fig. 2b that by feeding hydrogen
peroxide, the potential of the aqueous solution, initially containing
1.0 M V(II) ions, changes from 0.420 V to 0.846 V, meaning that
hydrogen peroxide can successively oxidize the V(II) ions to V(III),
V(IV), finally V(V) ions. The potential change roughly from 0.4 V to
0.8 V indicates that the discharge product at the cathode, V(IV) ions,
can be chemically charged to V(V) ions by hydrogen peroxide [14].
It should be noted that the two chemical reactions have very fast
reaction rates and can be completed within a few seconds, indi-
cating that the two chemical charge processes are not the limiting
factor for the power output of this fuel cell.
4.2. Electrochemical discharge
Fig. 3 shows the polarization and power density curves of the
zincehydrogen peroxide fuel cell at 60 ! C. It is seen that the open-
circuit voltage (OCV) and the peak power densities are 1.55 V and
1192 mW cm 2, respectively. Recently, Li and Dai [15] developed a
high-performance zinc fueled fuel cell based on hybrid electro-
catalysts, resulting in an OCV of 1.40 V and a peak power density of
265 mW cm 2. The peak power density achieved by the present
fuel cell is about five times higher than the state-of-the-art
 L. An et al. / Journal of Power Sources 275 (2015) 831e834
Fig. 2. Potentiometric titration of the vanadium ions. (a) V(V) to V(II) by Zn; (b) V(II) to
V(V) by H2O2.
performance achieved by conventional zinc fueled fuel cells. This
extraordinary improvement in performance can be mainly attrib-
uted to the fast kinetics of the electrochemical reactions between
vanadium redox couples. The previous studies have shown that the
exchange current densities of the oxidation reaction of the V(II)
ions (to V(III) ions) and the reduction reaction of the V(IV) ions (to
V(V) ions) are 20 mA cm 2 and 5 mA cm 2 [16], respectively. It
should be noticed from Fig. 3 that the IR-free polarization curve
Fig. 3. Polarization and power density curves of the zincehydrogen peroxide fuel cell.
833
suggests that the limiting factor in the performance is the ohmic
loss (Internal resistance: 306 mU cm2).
4.3. Zinc as a solar fuel
Fig. 4 shows the schematic of a sustainable transportation sys-
tem powered by solar energy. It can be seen that the commercial-
ization of EVs powered by the present fuel cell requires the
establishment of two other system elements, i.e.: a solar power
farm and the zinc regeneration industry. The discharge products,
ZnSO4, can be regenerated by electrolysis [17], which can be pow-
ered by solar cells, using the following chemical reaction:
Solar Power
2ZnSO4 þ 2H2 O ! 2Zn þ 2H2 SO4 þ O2 (6)
Regenerated zinc and sulfuric acid can be recycled to power EVs.
The overall efficiency of such a zinc regenerative fuel cell system
has been estimated to be 30%e50% and about 20%e40% for a
hydrogen regenerative fuel cell system [18].
5. Concluding remarks
In this work, we have proposed a catalyst-free, high-perfor-
mance zincehydrogen peroxide fuel cell that consists of a redox
flow cell with the respective redox couple at the anode and cathode
regenerated by the fuel (zinc) and the oxidant (hydrogen peroxide).
Potentiometric titrations have proved that zinc and hydrogen
peroxide can chemically charge the V(III) ions (to V(II) ions) and
V(IV) ions (to V(V) ions), respectively. By using V(II)/V(III) and V(IV)/
V(V) as the model redox couples in the anode and cathode,
respectively, we have demonstrated that the present fuel cell re-
sults in a peak power density of 1192 mW cm 2 at 60 # C, which is
about five times higher than that of conventional state-of-the-art
zinc fueled fuel cells (265 mW cm 2). In addition, the sole use of
carbon materials in preparing the fuel cell electrode makes it more
cost-effective and durable, thereby increasing the success of
widespread commercialization, particularly in electric vehicle ap-
plications. It is also recognized that the fuel for the present fuel cell,
Fig. 4. Schematic illustration of a sustainable transportation system powered by solar
energy.
834 L. An et al. / Journal of Power Sources 275 (2015) 831e834
zinc, can be a sustainable fuel regenerated with the electricity from
renewables such as solar and wind farms.
Acknowledgments
The work described in this paper was fully supported by a grant
from the Research Grants Council of the Hong Kong Special
Administrative Region, China (Project No. 623313).
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