Materials

Horizons
MINIREVIEW View Article Online
View Journal | View Issue

Magnesiumair batteries: from principle to

application
Cite this: Mater. Horiz., 2014, 1, 196
Tianran Zhang, Zhanliang Tao and Jun Chen*

Metalair batteries are important power sources for electronics and vehicles because of their remarkable
high theoretical energy density and low cost. In this paper, we introduce the fundamental principles and
Published on 10 September 2013. Downloaded on 12/12/2014 21:07:04.

Received 21st July 2013
Accepted 30th August 2013
DOI: 10.1039/c3mh00059a
rsc.li/materials-horizons
applications of Mgair batteries. Recent progress in Mg or Mg alloys as anode materials and typical
classes of air cathode catalysts for Mgair batteries are reviewed. In the meantime, dierent
compositions of the electrolyte are also compared. The design of electrode materials both for anodes
and cathodes of Mgair batteries is discussed for further performance improvement. It is noted that in
the development of rechargeable Mgair batteries, bi-functional catalysts with reversible oxygen
reduction and evolution reactions are facing challenges and it is worthwhile devoting much eort to this.

Anode: Mg / Mg2+ + 2e
(1)

Introduction
Metalair batteries have attracted much attention as prom- Cathode: O2 + 2H2O + 4e
/ 4OH
(2)
ising electrochemical energy storage and conversion devices
Total: 2Mg + O2 + 2H2O / 2Mg(OH)2 (3)
due to their high theoretical energy density and low cost.13
Among various types of metalair batteries, lithiumair and
zincair batteries have been investigated,47 while magnesium
During the discharge process, the anode Mg is oxidized to
(Mg)air batteries have not been explored as much. The basic
Mg2+, producing two electrons, while at the opposite electrode,
structure of a Mgair battery is shown schematically in Fig. 1,
O2 passes through the air cathode and is then reduced to OH

composed of an Mg (or Mg alloy) anode, an air cathode and a
by reaction with H2O and electrons.8 The theoretical voltage of
saline electrolyte. The reactions involved in Mgair batteries
the Mgair battery is 3.1 V and the specic energy density is 6.8
are as follows:
kW h kg
1, as summarized in Table 1. The Mgair battery is a
promising electrochemical energy storage and conversion
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education),
device since Mg is abundant on the earth, has a high reaction
College of Chemistry, Synergetic Innovation Center of Chemical Science and
Engineering, Nankai University, Tianjin 300071, China. E-mail: chenabc@nankai.
activity, is light weight, has low toxicity and has relatively high
edu.cn

Jun Chen is the Chair Professor

on energy materials chemistry at
Nankai University, the Director of
the Key Laboratory of Advanced
Energy Materials Chemistry
(Ministry of Education). He
received his B.S. and M.S.
degrees from Nankai University
in 1989 and 1992, respectively,
and his Ph.D. from Wollongong
University (Australia) in 1999. He
held the NEDO fellowship at the
National Institute of AIST Kansai
Center (Japan) from 1999 to 2002. His research activity focuses on
nanomaterials, electrochemistry, batteries, fuel cells and solar cells
with ecient energy storage and conversion. Fig. 1 Typical structure and working principle of an Mgair battery.

196 | Mater. Horiz., 2014, 1, 196206 This journal is The Royal Society of Chemistry 2014
 View Article Online

Minireview Materials Horizons

Table 1 Voltage and energy density comparison of selected batteries1

Theoretical cell
Selected batteries voltage (V vs. SHE) Theoretical specic energy densitya (kW h kg
1)

Li-ion (0.5C6Li + Li0.5CoO2 4 3C + LiCoO2) 3.8 0.387

Liair (2Li + O2 / Li2O) 2.91 13.0
Lisulfur (2Li + S 4 Li2S) 2.2 2.6 (ref. 4)
Znair (2Zn + O2 / 2ZnO) 1.65 1.3
Mgair (Mg + 0.5O2 + H2O / Mg(OH)2) 3.1 6.8
P
a
The theoretical specic energy density (3M
nFE/ M, where F is the Faraday constant, E is the reaction potential and M is the molar mass of
reactants) is calculated excluding O2 for metalair batteries.

safety.911 Generally speaking, the present Mgair battery is a stable below
2.37 V with a large pH range. Unfortunately, the
primary battery. Indeed, the Mgair battery can be re-used area is below the region of water stability. Mg2+ is the stable
Published on 10 September 2013. Downloaded on 12/12/2014 21:07:04.

mechanically by replacing the spent Mg anode and electrolyte substance in a pH range from 0 to 11, above which Mg(OH)2 is
with a fresh Mg anode and electrolyte, making it refuelable.12 the stable one. Consequently, in neutral and acidic aqueous
However, rechargeable Mgair batteries with reversible oxygen environments, Mg spontaneously converts to Mg ions. These
reduction and evolution reactions are facing challenges and it is further react with water through an electrochemical reaction to
worthwhile devoting much eort to this. produce magnesium hydroxide and hydrogen gas, oen
Though Mgair batteries have a relative high voltage and involving micro-galvanic coupling between cathodic areas
energy density, there are still scientic problems limiting their (where the electrochemical reduction of water happens) and
widespread application. The main issue of Mgair batteries is anodic areas (where the electrochemical oxidation of Mg
the high polarization and low coulombic eciency. For
example, the working voltage is normally below 1.2 V and the
practical specic energy is lower than ten percent of the theo-
retical one. This issue is caused by two aspects: the corrosion of
the Mg anode arising from the reaction of Mg and the electro-
lyte, and the sluggish kinetics of the oxygen reduction reaction
in the air cathode.
To overcome the existing problems of Mgair batteries, more
investigation and deep understanding are obviously needed.
Herein, we review Mgair batteries from basic principles to
applications. In particular, the corrosion mechanism of Mg, the
recent progress on Mg anode materials, the characterization of
the electrolyte, the air electrode structure and the catalyst
design for the oxygen reduction reaction are summarized to
provide a more in-depth understanding of Mgair batteries.
This should shed light on further research and design of the
electrodes, electrolytes, and structures for both primary and
rechargeable Mgair batteries. This review is organised in the
following sequence: the Mg anode, electrolyte, air cathode, and
applications are introduced, followed by conclusions.

Mg anode
The Mg anode plays a critical role in Mgair batteries. During
discharge, Mg in the anode is dissolved to produce Mg2+,
producing two electrons (eqn (1)). The standard electrode
potential of the reaction is
2.37 V and this electrochemical
reaction can produce 2.2 A h g
1 of capacity. However, for Mg
air batteries, a high level of polarization is displayed. One issue
is the side-reaction in the Mg anode, that is to say, the corrosion
of Mg. Therefore, in order to improve the performance of Mg
Fig. 2 (a) Pourbaix diagram for the magnesiumwater system at
air batteries, it is necessary to discuss the corrosion mechanism 25  C. Adapted from ref. 15. (b) Negative dierence eect (NDE) of
of the Mg anode. In the Pourbaix diagram of a Mgwater system magnesium. Reproduced from ref. 16 by permission. Copyright 2003,
at 25  C,13,14 as shown in Fig. 2a,15 Mg is thermodynamically Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

This journal is The Royal Society of Chemistry 2014 Mater. Horiz., 2014, 1, 196206 | 197

Materials Horizons
occurs).16 This process is the corrosion of Mg with the following
three parts:
Mg / Mg2+ + 2e
(anodic reaction) (4)
2H2O + 2e
/ H2 + 2OH
(cathodic reaction) (5)
Mg2+ + 2OH
/ Mg(OH)2 (product formation) (6)
The overall corrosion reaction can be written as:
Mg + 2H2O / Mg(OH)2 + H2 (7)
Among these reactions, the hydrogen evolution reaction (HER)
(eqn (5)) is the limiting factor to the corrosion of Mg.
Published on 10 September 2013. Downloaded on 12/12/2014 21:07:04.
Besides the HER, other factors also give rise to the corrosion
of Mg. The negative dierence eect (NDE) is an important one.
Generally, the corrosion reaction is either an anodic or cathodic
process. For most metals such as iron, zinc or steel, when the
applied potential increases, the anodic current rises, accom-
panied by the cathodic current decreasing simultaneously (Ia
and Ic curves in Fig. 2b). However, Mg displays quite dierent
behaviour. It is clearly shown in Fig. 2b that the anodic current
IMg (corresponding to eqn (4)) and the cathodic current IH
(corresponding to eqn (5)) both rise with an increase of the
applied potential. This strange performance of Mg is called the
negative dierence eect (NDE). As the NDE increases the
hydrogen evolution current, it accelerates the corrosion of Mg.
The reasons for the NDE have been investigated for decades and
dierent possible mechanisms are proposed. However, none of
the mechanisms can completely interpret the NDE.16,17
Another factor of Mg corrosion is galvanic corrosion, which
is caused by the impurities in Mg plate such as metallic iron,
nickel, or copper. These elements construct micro-cells with Mg
and expedite the cathodic reaction in eqn (5), resulting in
further corrosion of the Mg plate.8 It is found that the galvanic
corrosion is directly associated with the impurity content.16 In
particular, once the impurity content exceeds the tolerance
limit, the corrosion rate is greatly increased while with a lower
impurity content, the corrosion rate remains low. For example,
the tolerance limits of Fe, Ni, and Co are about 0.2 wt%,16
indicating that trace amounts of these elements are harmful
to Mg.
According to the discussions above, the HER and NDE as
well as impurities are the main factors for the corrosion of Mg. A
suitable Mg anode material requires a lower HER reaction rate,
a smaller NDE and no impurities. Meanwhile, the by-product
Mg(OH)2 (eqn (7)) should also be easily removed from the
anode in order to gain refreshed active sites. Therefore,
searching for new Mg-based anode materials with high reaction
activity and slow corrosion rate is important for the develop-
ment of Mgair batteries. So far, eorts have focused on two
directions as summarized in Table 2. One is alloying Mg with
other metals to inhibit the HER and the other is to improve the
properties of Mg itself.
Alloying Mg with other metals such as Al, Mn, or Zn, which
prevent the hydrogen evolution reaction, has attracted a lot of
attention. With the fast development of metallurgical
198 | Mater. Horiz., 2014, 1, 196206
View Article Online
Minireview
technology, Mg alloys have been widely explored for Mg
seawater batteries.22,23 The eect of alloyed metals on the
corrosion rate of Mg alloys has been deeply investigated.15 One
of the most interesting series of Mg alloys is MgAl alloys. In the
phase diagram of MgAl alloys,24 when the concentration of Al is
lower than 10 wt%, the Mg phase is obtained aer solidication
with a hexagonal closely-packed hcp structure. The Al intro-
duced to the Mg will not only enhance the physical strength but
also prevent the HER. Therefore, MgAl alloys suppress the self-
corrosion of the anode.
Meanwhile, the addition of a small amount of zinc to MgAl
alloys to produce MgAlZn alloys such as AZ31, is widely
employed for Mgair batteries. The discharge testing of AZ31 in
neutral 3.5 wt% NaCl solution with 5 mA cm
2 current density
shows that the operating voltage is 1.125 V and the specic
discharge capacity is 1125 mA h g
1.18 In comparison with AZ31,
the same type of AZ61 shows better performance in Mgair
batteries with a 7 wt% NaCl electrolyte, where the cell voltage is
about 1.28 V.12
Moreover, MgAl alloys containing manganese are also an
important option. The existence of manganese reduces the
particle size of the alloys. The performances of AM50, AM60,
and MA8M06 as anode materials of Mgair batteries have been
investigated, among which MA8M06 is the best one with a
higher voltage and more positive corrosion potential even than
the AZ series alloys.20
Recently, alloying Mg with Li has been considered for
potential battery anodes due to the more negative standard
potential and high Faradic capacity, as well as the high specic
energy of MgLi alloys.18,21 Taking Mg14Li1Al0.1Ce as an
example, a higher electrochemical activity and lower self-
corrosion rate are observed than for Mg and AZ31. Fig. 3
shows the discharge behaviour of Mgair batteries with Mg
14Li1Al0.1Ce, pure Mg, and AZ-31 as the anodes at a current
density of 2.5 mA cm
2. The specic capacity of the Mgair cell
with Mg14Li1Al0.1Ce anode in 3.5 wt% NaCl solution is
2076 mA h g
1 and its operating voltage is 1.272 V, higher than
that with pure Mg and AZ-31 anodes.18 In summary, Mg alloys
show high performance as anode of Mgair batteries. However,
Mg alloys still suer from corrosion, leading to lower working
voltages in comparison with the theoretical ones. Thus, it is still
necessary to further reduce the corrosion rate and improve the
reaction activity of the anode.
Another strategy to improve the performance of the Mg
anode is to modify the intrinsic properties of Mg itself. In this
case, the purity and morphology are important factors. As
mentioned above, commercial Mg plate contains harmful
impurities such as Fe, Co or Ni. Reducing the amount of
impurities in the Mg plate is helpful for improving the perfor-
mance of Mgair batteries. High-purity Mg (99.99%) shows
better performance as an anode with higher corrosion resis-
tance (meaning lower corrosion rate) than even some Mg
alloys.20
In addition to just suppressing the corrosion, increasing
the activity of the anode is also important. It is accepted that
nanostructures exhibit novel physical and chemical properties
that are not present in the corresponding macroscale
This journal is The Royal Society of Chemistry 2014

Minireview
Table 2 Types of Mg anode for Mgair batteries
Type Main constituents
Simple Mg Commercial Mg Mg
Nano/mesoscale Mg Mg
Mg-alloy AZ31, AZ61, AZ91a Mg/Al/Zn
AM50, AM60, MA8M06b Mg/Al/Mn
Published on 10 September 2013. Downloaded on 12/12/2014 21:07:04.
MgLi alloys Mg/Li
a
AZ31 (96 wt% Mg, 3 wt% Al and 1 wt% Zn), AZ61 (93 wt% Mg, 6 wt% Al and 1 wt% Zn), AZ91 (90 wt% Mg, 9 wt% Al and 1 wt% Zn). b AM50 (94 wt%
Mg, 5 wt% Al, 0.6 wt% Mn), AM60 (93 wt% Mg, 6 wt% Al, 0.6 wt% Mn), MA8M06 (97 wt% Mg, 1.3 wt% Mn, 0.12 wt% Zn, 0.12 wt% Al, 0.2 wt% Fe).
Fig. 3 Discharge behaviour of Mgair batteries with dierent anode
materials at a current density of 0.5 mA cm
2. Reproduced from ref. 18
by permission. Copyright 2011, Elsevier.
structures.25,26 Furthermore, nanomaterials have already been
investigated in batteries and fuel cells.2729 In Mgair batteries,
with controllable morphology, Li et al. explored the electro-
chemical activity of micro/nanostructured Mg anodes in Mgair
cells.19 Samples with microspheres, microplates, nanorods and
sea-urchin-like nanostructures prepared by the vapour-
transport method have shown better performance in compar-
ison with that of commercial Mg powders in the Mg(NO3)2 +
NaNO2 electrolyte (Fig. 4). Among the micro/nanostructures,
sea-urchin-like Mg displays the highest energy density and
high-rate performance. The results demonstrate that porous
and network nanostructures increase the number of active sites
and accelerate the sedimentation of the by-product (Mg(OH)2)
in a certain electrolyte, and hence improve the performance of
the Mgair battery. One thing that should be mentioned is that
This journal is The Royal Society of Chemistry 2014
View Article Online
Materials Horizons
Morphology Properties Ref.
High corrosion rate, large negative 1
dierence eect
Nanospheres Better corrosion resistance and high 19
Nanoplates current density as well as higher rate
Nanorods discharge ability than commercial Mg
Urchin-like
Better corrosion resistance, better 12 and 18
strength and tarnish resistance and
higher working voltage than commercial
Mg
Better corrosion resistance, smaller 20
crystalline grains and higher working
voltage than commercial Mg
Better corrosion resistance, higher 18 and 21
energy density and higher working
voltage than commercial Mg
a high specic area of the Mg anode does enhance the activity of
the cell reaction, but at the same time it also increases the
corrosion rate of Mg. Therefore, just tuning the Mg anode is not
enough and a suitable electrolyte is highly desired, which is
discussed later.
According to the previous eorts on Mg anode materials, it
is concluded that for developing Mg anodes with high-
performance, a small size of Mg particles, especially with
nanostructures, promotes the reaction activity. The high
specic surface of Mg particles results in more Mg atoms being
exposed to the electrolyte and the amount of Mg(OH)2 by-
product is reduced quickly. In the meantime, Mg alloying
with elements such as Al, Mn or Li suppresses the HER and
reduces the self-corrosion of Mg. Therefore, hollow or porous
nanostructures of Mg or Mg alloys should be promising
candidates for Mgair batteries. Moreover, with the rapid
development of computer technology, rst-principles calcula-
tions have been widely used for designing materials, especially
for batteries.30,31 For Mg-based materials, eorts have been
devoted to energy storage and the electronic structures of Mg
alloys.8,32,33 It is expected that using calculations as a tool,
functional Mg anode materials are to be designed.
Electrolyte
In general, the electrolyte of an Mgair battery is a neutral saline
aqueous solution that contacts with the electrodes, greatly inu-
encing the electrode reactions. Since the high polarization and
low coulombic eciency of the Mgair battery is not only related
to the electrodes but also to the electrolyte, choosing a suitable
electrolyte is crucial to the performance of Mgair batteries.
For the anode reaction, the electrolyte has a large inuence
on the corrosion of Mg. Table 3 summarizes the corrosion
potential of bare Mg in various aqueous solutions. It is clear
that Mg has a higher resistance in alkaline solution than in
Mater. Horiz., 2014, 1, 196206 | 199

Materials Horizons
Published on 10 September 2013. Downloaded on 12/12/2014 21:07:04.
Fig. 4 Typical scanning electron microscopy (SEM) images of as-
prepared Mg: (a) microspheres, (b) microplates, (c) nanorods, (d) sea-
urchin-like nanostructures. (e) Representative transmission electron
microscopy (TEM) image of nanorods and (f) high-resolution trans-
mission electron microscopy (HRTEM) image of the white square
marked in (e) with the inset showing the corresponding fast Fourier
transform (FFT) pattern. (g) Representative discharge curves of the
Mgair batteries made from Mg microspheres and sea-urchin-like
nanostructures at a constant current of 0.5 mA and a temperature of
25  C. Reproduced from ref. 19 by permission. Copyright 2006, Wiley-
VCH Verlag GmbH & Co. KGaA, Weinheim.
acidic or neutral solution. Recent research also shows that by
tuning the pH value above 10, an electrolyte consisting of a
near-saturated aqueous solution of LiCl, MgCl2 or mixture of
the two salts can suppress the hydrogen evolution reaction and
promote the corrosion resistance of Mg.34 The reason for the
high corrosion resistance of Mg in the alkaline solution is due
200 | Mater. Horiz., 2014, 1, 196206
View Article Online
Minireview
Table 3 Rest potential (Er) of Mg with various aqueous solutions35
Electrolyte Er (V vs. NHE)
NaCl
1.72
Na2SO4
1.75
HCl
1.68
HNO3
1.49
NaOH
1.47
NH3
1.43
to the partial formation of Mg(OH)2 lm on the surface of the
Mg or Mg alloys. This could protect the anode active material
from corrosion. However, too much Mg(OH)2 lm on the elec-
trode prevents further reaction of the anode, leading to a
delayed response to an increase in the load.1 Thus, a neutral
electrolyte is usually used in Mgair batteries.
In addition to the inuence of pH, the anions in the aqueous
solution also play an important role. A large number of electro-
lytes containing dierent anions have been screened with the
purpose of understanding the inuence of the anions.36 Upon
comparison with NaCl, KHCO3, NH4NO3, NaNO3, NaNO3 +
HNO3, Mg(NO3)2$6H2O + NaNO2, NaNO2, Na2SO4, MgCl2, and
MgBr2, the Mg(NO3)2$6H2O + NaNO2 electrolyte can result in low,
uniform corrosion and low anodic polarization of Mg at useful
current densities as well as fast coagulation of the by-products
(Mg(OH)2).19 It has been found that Cl
and SO42
are more
likely to attack Mg and thus lead to high corrosion rates, while
NO3
or NO2
ions, though they also attack magnesium, do not
do so to the same extent as chlorides.17 Therefore,
Mg(NO3)2$6H2O + NaNO2 is more suitable than other salts.
Another factor related to the electrolyte is the concentration of
salt in the electrolyte. The corrosion rate of pure Mg in seawater is
about 0.25 mm per year while that in 3 M MgCl2 solution is 1200
times larger.35 Therefore, a low concentration of salt is usually
necessary. Also, adjusting the metal/electrolyte interface is a
relevant method to promote resistance to corrosion. Khoo et al.37
used phosphonium chloride ionic liquid and water as an elec-
trolyte and tested the discharge performance of an Mgair
battery. The results demonstrated that the amorphous gel-like
interface formed on Mg led to a level of passivation when the
cell was at open circuit. This stabilized the metal/electrolyte
interface and enhanced the performance of the Mgair battery.
In addition to searching for new electrolytes, some hydrogen
evolution inhibitors such as stannates, quaternary ammonium
salts, dithiobiuret and their mixtures can be added into the
electrolyte to suppress the HER. A mixture of stannate and
quaternary ammonium salt can improve the eciency of the
AZ31 alloys, leading to a higher voltage potential.8 Therefore, it
is worth engaging in research focused on developing inhibitors
for the HER.
Air cathode
The performance of Mgair battery is tightly associated with the
air cathode. The structure of a typical air cathode is composed
by four layers: a waterproof breathable layer, a gas diusion
This journal is The Royal Society of Chemistry 2014

Minireview
Fig. 5 Structure of a typical air cathode with four layers.
layer, a catalyst layer and a current collector layer, as shown in
Fig. 5. The waterproof layer is usually a water-repellent porous
substance (e.g. paran wax or Teon), which is used to separate
the electrolyte and air, and at the same time, is permeable only
Published on 10 September 2013. Downloaded on 12/12/2014 21:07:04.
to O2 and blocks CO2 and H2O. The gas diusion layer has a
highly porosity and high electronic conductivity, and is usually
made from acetylene black containing hydrophobic materials
such as polytetrauoroethylene (PTFE). The catalyst layer is
composed of active catalysts for the oxygen reduction reaction
(ORR), which are dispersed in the surface of the gas diusion
layer near the electrolyte. The commonly used catalysts are
noble metals (Ag). In addition to the anode corrosion, the low
coulombic eciency of the Mgair battery is attributed to the
overpotential of the air cathode caused by the sluggish kinetics
of the ORR. Therefore, it is essential to improve the perfor-
mance of the air cathode.
In a neutral electrolyte, oxygen is reduced to OH
at the
interface of the gassolidliquid ternary phases in the air
cathode. As the ORR occurs in the three-phase interface, it
involves complex physical and chemical reactions. In general,
the possible reaction pathways involved in the ORR in a neutral
solution can be expressed as:38
O2 + 2H2O + 4e
/ 4OH
(8)
O2 + H2O + 2e
/ HO2
+ OH
(9)
HO2
+ H2O + 2e
/ 3OH
(10)
2HO2
/ 2OH
+ O2 (11)
The standard electrode potential of the oxygen reduction
reaction (eqn (8)) is 0.44 V. However, a large overpotential and
high polarization are usually observed for the reaction, leading
to a bad performance of the Mgair battery. This is due to the
sluggish kinetics of the ORR. Therefore, to lower the over-
potential, highly ecient catalysts are required. As the direct
four-electron process (eqn (8)) is the most ecient, a suitable
catalyst should have direct four-electron catalytic ability. Addi-
tionally, the catalyst should be abundant on the earth and have
a low cost.
Many types of catalysts have been investigated for the ORR,
either in acidic or alkaline solutions. However, research focused
on developing catalysts for neutral solutions is limited.
According to previous literature,39 the performances of catalysts
in neutral solutions are comparable to that in weak alkaline
solution. Therefore, the catalysts suitable for weak alkaline
This journal is The Royal Society of Chemistry 2014
View Article Online
Materials Horizons
solutions are also suitable for neutral solutions. Herein, we only
briey review the catalysts used in neutral and alkaline solu-
tions while those for acidic solutions have been discussed in
other comprehensive reviews.3,38
The catalysts used for metalair batteries are summarized in
Table 4. Among these, platinum shows superior ORR catalytic
activity. The eects of particle size and crystal plane have been
considered, showing that a catalyst consisting of carbon sup-
ported 24 nm Pt particles with the (111) surface is the state-of-
the-art ORR catalyst.40,41 However, the high price and the scar-
city of Pt results in a high cost of the metalair battery, meaning
that the search for low Pt and non-Pt catalysts receives a lot of
attention.38
For low-Pt catalysts, alloying Pt with other cheap transition
metals has attracted much attention, due to better activity than
pure Pt. With the help of spectroscopy and theoretical calcula-
tion,42 the reason for the enhanced activity of Pt-alloys is well
understood and a trend for their ORR activity is proposed, as
shown in Fig. 6a. The tight binding of the intermediates such as
OH* and O* on the surface is the main reason for the activity
attenuation of Pt-based catalysts.43 The weakening the O* and
OH* adsorption, which are good descriptors for ORR activity, is
a principle reason for the higher activity of Pt alloys. According
to Fig. 6a, a better catalyst should involve O atom binding
strengths 00.4 eV weaker than the Pt (111) surface with the
optimum value at about 0.2 eV. Based on these ndings, the
Pt3Y alloy is outstanding with the highest activity.42 Moreover,
the O adsorption energy is also related to the Pt d-band-center,
where lowering the d-band-center can result in faster PtO
electro-reduction and increase the ORR kinetics.44 For example,
X-ray absorption near edge structure (XANES) measurements of
PtCo/C indicate a lower variation of the Pt 5d band vacancy from
lower to higher potentials due to the presence of Co. This
increases the Pt electronegativity and decreases the PtOH
coverage, resulting in a higher catalytic activity than Pt/C.45
Besides, tuning the morphology and structure of Pt alloys also
enhances the activity and stability toward the ORR. A spongy
structure with numerous voids is obtained via chemical deal-
loying of intermetallic nanoparticles of Cu3Pt, resulting in
enhanced specic and mass activities and higher stability
relative to Pt/C.46 Recently, a new class of PtCo nanocatalysts
composed of ordered Pt3Co intermetallic cores with a 23
atomic-layer-thick Pt shell has been developed with high activity
and stability, which is attributed to the Pt-rich shell and espe-
cially to the stable intermetallic Pt3Co core arrangement.47 This
provides a new direction for catalyst performance optimization.
Furthermore, some new and low cost preparation methods of Pt
alloys have been developed. Using Pt3Fe nanoparticles as an
example, a surfactant-free NPKCl matrix method (NP stands
for nanoparticle) has been developed for the synthesis of
nanoparticles with controlled sizes and structures. Insoluble
KCl serves as a matrix that avoids particle agglomeration and
controls the coalescence of nanoparticles during thermal
annealing.48 One thing that should be mentioned is that the
transition metals (Fe, Co, Ni) in Pt-alloys, which may be dis-
solved during the ORR, have little eect on the Mg anode. In the
Mg anode, the impurities are Fe, Ni and Co metals, while the
Mater. Horiz., 2014, 1, 196206 | 201
 View Article Online

Materials Horizons Minireview

Table 4 Types of cathode catalysts for Mgair batteries in neutral or alkaline solutions

Type Representative examples Remarks Ref.

Noble metals Pt-based Pt High catalytic activity; low 40

overpotential and large
limited current density; four-
electron reaction
mechanism; commercially
used catalyst; high price and
scarcity; not quite stable
Pt alloys Higher activity than pure Pt; 4551
four-electron reaction
mechanism; lower price;
better stability
Non-Pt Pd, Au, Ag,. Lower activity than Pt; four 5254
electron reaction
Published on 10 September 2013. Downloaded on 12/12/2014 21:07:04.

mechanism; high price and

Carbon-based materials
Transition metal oxides
N-containing metallic
complex
a
r-GO is reduced graphene oxide. b N-GA is N-doped graphene aerogel. c CoPcF16 is uorinated cobalt phthalocyanine.
scarcity
Non-Pt alloys Higher activity than pure 5557
noble metals and
comparable to Pt; four-
electron reaction
mechanism; lower price
Carbons Porous carbon, nanotubes, Much higher overpotential
graphene and smaller limited current
density than metals; two-
electron reaction
mechanism; better stability;
usually used as substrates
Modied carbons N-doped graphene, N-doped Much improved catalytic 5863
nanotubes, P-doped activity over pure carbons
graphene,. and close to Pt; quasi-four-
electron reaction
mechanism; better
durability; promising
substitute for noble metal;
dicult to produce
Pure oxides MnOx, CaMnO3, Lower electrocatalytic 39 and 6466
CoMn2O4,. activity than Pt; serial two-
electron plus two-electron
mechanism; stable; low cost;
bad electronic conductivity
Complexes Co3O4/r-GO,a MnCoO/r-GO,a High activity and 6769
Fe3O4/N-GAs,b. comparable to Pt; improved
electron conductivity over
metal oxides; four-electron
reaction mechanism; stable;
promising substitute for
noble metal
FeTMPP/C, CoTMPP/C, CoPcF16@Ag/C,.c High activity and 70 and 71
comparable to Pt/C; better
durability than Pt; low cost;
four-electron reaction
mechanism

cathodic dissolved transition metal is mainly in the form of ion
states. As interpreted above, Fe, Ni and Co metals facilitate the
hydrogen evolution reaction due to the construction of micro-
cells with Mg, but the ion states (Fe2+, Co2+ and Ni2+) cant
form such micro-cells. Therefore, these transition metals in Pt-
alloys will not induce the corrosion of the Mg anode.
In addition to Pt-based materials, other noble metals such as
Pd, Cu and Ag or their alloys achieve much attention as ORR
catalysts with the activity trend shown in Fig. 6b. Though non-Pt
noble metals such as Ag are not comparable with Pt,72 their
much lower cost makes them candidates for the ORR. A carbon-
supported Ag catalyst exhibits a high ORR activity with a
predominately four-electron reaction mechanism in 0.1 M
NaOH solution. Upon increasing the loading amount of Ag, a
more positive initial potential is obtained, indicating better
catalytic properties.73 Furthermore, non-Pt alloys exhibit higher

202 | Mater. Horiz., 2014, 1, 196206 This journal is The Royal Society of Chemistry 2014

Minireview
Published on 10 September 2013. Downloaded on 12/12/2014 21:07:04.
Fig. 6 Trends in oxygen reduction activity plotted as a function of the
O binding energy of (a) Pt skins, reproduced from ref. 42 by
permission (copyright 2009, Macmillan Publishers Limited) and (b)
metals, reproduced from ref. 72 by permission of the American
Chemical Society.
activities. For example, with Ag-rich AgPd nanoalloys, the ORR
mass activities per total amount of metal are 1.6, 2.7 and 3.2
times that for pure Pd for AgPd2, Ag9Pd and Ag4Pd alloys,
respectively.74
To further control the cost of Mgair batteries, much
research is devoted to developing non-noble metal catalysts
such as carbon-based materials and transition metal oxides.
Carbon materials are ubiquitous in air electrodes in Mgair
batteries, not only as catalysts and conductive agents but also as
a gas diusion layer. For catalysts, carbon involves a two-
electron reaction with the production of H2O2. This reaction
has sluggish kinetics, so carbon materials alone are not good
ORR catalysts. However, by doping with heteroatoms (P or N),
the ORR activities of the carbons improve a lot, especially for
high surface areas such as mesoporous carbons58,59 and nano-
tubes,61 as well as graphene.62,63,75 For instance, vertically
aligned nitrogen-containing carbon nanotubes (VA-NCNTs)
display much better electrocatalytic activity and long-term
operation stability than platinum in alkali with a four-electron
reaction process, as shown in Fig. 7. The presence of nitrogen,
which imparts a high positive charge on adjacent carbon atoms,
plays an important role for activity enhancement.61 A similar
result is also obtained in the case of N-containing graphene.62
These results indicate that N-doped high surface area carbon
This journal is The Royal Society of Chemistry 2014
View Article Online
Materials Horizons
Fig. 7 (a) CVs for oxygen reduction at the unpuried (upper) and
electrochemically puried (bottom) VA-NCNT/GC electrodes in
argon-protected (dotted curves) or air-saturated 0.1 M KOH (solid red
curves) at a scan rate of 100 mV s
1. Rotating Ring-Disk Electrodes
(RRDE) plots and the corresponding amperometric responses for the
oxygen reduction in air saturated 0.1 M KOH at (b) NA-CCNT/GC
(curves 1 and 10 ), PtC/GC (curves 2 and 20 ), and NA-NCNT/GC (curves
3 and 30 ) electrodes and at (c) PtC/GC (curve 1), VA-CCNT/GC
(curve 2), and VA-NCNT (curve 3) electrodes. (d) Calculated charge
density distribution for NCNTs. (e) Schematic representations of
possible adsorption modes of an oxygen molecule at CCNTs (top) and
NCNTs (bottom). VA-NCNT, NA-CCNT and GC stand for vertically
aligned nitrogen-containing carbon nanotubes, nitrogen-free
nonaligned carbon nanotubes and glass carbon, respectively. Repro-
duced from ref. 61 by permission of AAAS.
materials are promising substitutes for Pt. The eects of
dierent types of nitrogen are denite. Graphitic N determines
the limiting current density, while pyridinic N improves the
onset potential.63 However, one thing that should be mentioned
is that as the production of graphene and nanotubes is still
costly, much eort should be further devoted to a more facile
and lower cost synthesis of graphene and nanotubes.
Transition metal oxides are another important family of non-
noble metal ORR catalysts.38 The ORR activities of dierent
kinds of transition metal oxides have been thoroughly investi-
gated from their crystallographic structures, morphologies and
doping eects. Taking MnO2 as an example, the ORR properties
become worse for dierent MnO2 phases as follows: a- > b- > g-
MnO2, and nanostructures are superior to microstructures.64
Meanwhile, doping MnO2 with Cu or Ni improves the catalytic
activity.76 In order to accelerate the development of highly active
transition metal oxide catalysts, a design principle has been
identied. For perovskite, eg-lling with a value of 1 exhibits the
maximum activity due to stabilization of the O22
/OH

exchange, which is the rate-limiting step. However, an impor-
tant hindrance for transition metal oxides is the low electronic
conductivity. To improve this, constructing transition metal
oxides with highly conductive materials such as graphene or
porous carbons is a useful strategy. Although transition metal
Mater. Horiz., 2014, 1, 196206 | 203

Materials Horizons
oxides or carbons alone have low catalytic activity, their hybrids
show an unexpected, surprisingly high ORR activity due to
synergetic chemical coupling eects.67,69,77 Similar to Co3O4/N-
doped graphene, they exhibit a similar catalytic activity but
superior stability to Pt in alkaline solutions, as shown in Fig. 8.
The ORR activity of this hybrid is further improved by tuning
the morphology of the carbons.67 Moreover, this hybrid also
displays a high oxygen evolution reaction (OER) activity.68
It should be noted that N-containing metal macrocyclic
compounds are also important catalysts for the ORR. Cobalt
and iron tetramethoxyphenylporphyrin (CoTMPP and FeTMPP)
catalysts loaded on carbons or with preheating show high ORR
activity in alkaline solutions.7880 CoTMPP is more stable and
catalyzes oxygen reduction through a two-electron process, and
Published on 10 September 2013. Downloaded on 12/12/2014 21:07:04.
is more active than FeTMPP. In addition to tetramethoxy-
phenylporphyrins, other metal macrocyclic compounds have
been produced recently. For example, a new series of trinuclear
metal N4 complexes [MN4]n on carbon black have been
successfully prepared, revealing much better electrochemical
activity and long-term stability than the commercially available
Pt/C catalyst in an alkaline electrolyte.70
There are certainly many other catalysts such as nitrides for
the ORR.81 One can see that catalysts such as N-doped graphe-
nes are already comparable to Pt. Further decreasing the cost
and increasing the durability of the catalysts, especially in a
neutral solution, is the required direction for developing
cathode catalysts in Mgair batteries.
Applications
The application of Mgair batteries has a long history. As early
as the 1960s, General Electric (GE), an American company,
obtained a neutral NaCl solution Mgair fuel cell. Nowadays, an
important application of Mgair batteries is as backup systems
Fig. 8 (a) SEM images and (b) TEM images of Co3O4/N-rmGO hybrid.
(c) Oxygen reduction polarization curves and (d) chronoamperometric
responses (percentage of current retained versus operation time) of
Co3O4/rmGO, Co3O4/N-rmGO and Pt/C. rmGO stands for reduced
mildly oxidized graphene oxide. Reproduced from ref. 68 by permis-
sion. Copyright 2011, Macmillan Publishers Limited.
204 | Mater. Horiz., 2014, 1, 196206
View Article Online
Minireview
for electric and solar power, which can be employed in hospitals
and schools for emergencies. In the period in which the
batteries are not used, they are stored in the dry state for a long
time. When they are to be used, the electrolyte is added to the
batteries. Such easy operation makes their use convenient.
Recently, the Canadian Greenvolt Power Company successfully
developed a serial Mg/saltwater/air fuel cell (MASWFC),82 which
had a much higher energy density than a leadacid battery. This
system could provide electronic energy not only for TVs and
phone cells but also for vehicles. Another Canadian company,
MagPower Systems, also developed a Mgair battery
combining magnesium, oxygen and a saltwater electrolyte.83 In
this system, hydrogen inhibitors were added to prevent
hydrogen generation, showing an eciency rate of 90% and an
operating range of
20  C to 55  C. Potential markets for this
Mgair battery include remote military and telecommunication
sites. In the meantime, this system can also be used as a backup
system for electric and solar power devices.
Another important application of Mgair batteries is for
undersea instruments. Such a system employs Mg alloys as the
anode, seawater as the electrolyte and the oxygen dissolved in
seawater as the cathode. In 1996, Norway and Italy cooperatively
developed a Mgair fuel cell, which was used in the automatic
control systems for oshore oileld exploration.8 The fuel cell
was composed of two large piles with an energy density of 650
kW h and a life of 15 years. Undersea cells are also utilized in
lighthouses, oats and undersea monitoring equipment.
Meanwhile, the Mgair battery is an option for military appli-
cation. The Navy considered the potential of a hybridized Mg
air fuel cell and nickelzinc battery as energy providers for
detectors, which could provide 25 kW of pulse power over two
weeks.84
Conclusions
In this review, we highlight recent progress in Mgair batteries
from fundamental principles to the available applications. Mg
air batteries contains three parts: a Mg anode, an air cathode
and a saline neutral aqueous electrolyte. The reactions involved
in the batteries are Mg electrochemical oxidation to Mg ions in
the anode and the oxygen reduction reaction in the cathode. Mg
plates are common materials for the Mg anode and the draw-
back is the high level of corrosion. Mg alloys and Mg nano-
particles can improve the performance of the Mg anode. The air
cathode contains four layers and the sluggish kinetics of the
ORR hinders the performance of the cathode. Therefore, cata-
lysts as well as multilayer structures play a key role in the air
cathode. Noble metals such as Pt and Ag are the usual catalysts
in the air cathode. To lower the cost, dierent types of catalyst
such as N-doped carbonaceous, metal oxides and metal oxide
carbonaceous mixtures are used as substitutes for noble metals.
The neutral electrolyte consists of salts such as NaCl, NaNO2
and KHCO3, among which a mixed electrolyte containing
Mg(NO3)2$6H2O and NaNO2 shows a high performance. The
applications of Mgair batteries currently include undersea
equipment, military and backup systems.
This journal is The Royal Society of Chemistry 2014

Minireview
High polarization and low coulombic eciency are the main
problems of Mgair batteries. Methods to overcome these issues
mainly include searching for electrode materials with high
activities and low corrosion rates. For the anode, further eorts
will be devoted to searching for high hydrogen overpotential
elements for alloys, increasing the number of active sites and
utilization of Mg through structure design, and optimizing the
preparation process. For the cathode, the directions to be taken
are lowering the cost of the catalysts by searching for new
catalysts, improving the activity and durability of the catalysts
through hybrid technology, and increasing the contact between
oxygen, electrolyte and catalyst by tuning the multilayer struc-
ture. At the same time, the exploration of highly stable elec-
trolytes is also important.
Published on 10 September 2013. Downloaded on 12/12/2014 21:07:04.
It should be noted that currently Mgair batteries are
primary batteries. The production of rechargeable Mgair
batteries is still challenging. Compared with primary Mgair
batteries, rechargeable Mgair batteries are quite dierent, and
reversible oxygen reduction reactions and oxygen evolution
reactions are taking place. A non-aqueous system, which is
similar to that for a rechargeable Liair battery, should be a
good choice. Possible directions for developing rechargeable
Mgair batteries would focus on the following points: (1) the
rst and most important mission is to nd a fully rechargeable
Mg-base material. As we know, magnesium oxide is not quite
rechargeable, and magnesium peroxide may be a candidate due
to higher activity. (2) Searching for a suitable electrolyte that is
stable and does not react with the discharged products. In this
case, it is important to investigate the electrolyte of recharge-
able Mg-ion batteries. (3) Exploring electro-catalysts that are
highly active to both the oxygen reduction reaction and oxygen
evolution reaction, which reduce the polarization of the cell and
accelerate the decomposition of the discharged products.
Though many diculties are faced, it is still worth applying
much eort to develop rechargeable Mgair batteries.
Acknowledgements
This work was supported by the Programs of National 973
(2011CB935900), NSFC (21231005), 111 Project (B12015), and
Tianjin High-Tech (13JCQNJC06400).
References
1 D. Linden and T. B. Reddy, Handbook of Batteries, McGraw-
Hill, New York, 2002.
2 M. Armand and J. M. Tarascon, Nature, 2008, 451, 652657.
3 F. Y. Cheng and J. Chen, Chem. Soc. Rev., 2012, 41, 2172
2192.
4 P. G. Bruce, S. A. Freunberger, L. J. Hardwick and
J. M. Tarascon, Nat. Mater., 2012, 11, 1929.
5 G. Girishkumar, B. McCloskey, A. C. Luntz, S. Swanson and
W. Wilcke, J. Phys. Chem. Lett., 2010, 1, 21932203.
6 P. Sapkota and H. Kim, J. Ind. Eng. Chem., 2009, 15, 445450.
7 J. S. Lee, S. Tai Kim, R. Cao, N. S. Choi, M. Liu, K. T. Lee and
J. Cho, Adv. Energy Mater., 2011, 1, 3450.
This journal is The Royal Society of Chemistry 2014
View Article Online
Materials Horizons
8 W. Yang, S. Yang, G. Sun and Q. Xin, Chin. J. Power Sources,
2005, 29, 182186.
9 B. Peng, J. Liang, Z. Tao and J. Chen, J. Mater. Chem., 2009,
19, 28772883.
10 D. Aurbach, Z. Lu, A. Schechter, Y. Gofer, H. Gizbar,
R. Turgeman, Y. Cohen, M. Moshkovich and E. Levi,
Nature, 2000, 407, 724727.
11 X. Wang, Y. Hou, Y. Zhu, Y. Wu and R. Holze, Sci. Rep., 2013,
3, 1014.
12 R. P. Hamlen, E. C. Jerabek, J. C. Ruzzo and E. G. Siwek,
J. Electrochem. Soc., 1969, 116, 15881592.
13 M. Pourbaix, Atlas Dequilibres Electrochimiques, Gauthier
Villars, Paris, 1963.
14 G. G. Perrault, J. Electroanal. Chem. Interfacial Electrochem.,
1974, 51, 107119.
15 B. A. Shaw, Corrosion Resistance of Magnesium Alloys, ASM
International, 2003.
16 G. Song and A. Atrens, Adv. Eng. Mater., 2003, 5, 837858.
17 G. L. Song and A. Atrens, Adv. Eng. Mater., 1999, 1, 1133.
18 Y. Ma, N. Li, D. Li, M. Zhang and X. Huang, J. Power Sources,
2011, 196, 23462350.
19 W. Li, C. Li, C. Zhou, H. Ma and J. Chen, Angew. Chem., Int.
Ed., 2006, 45, 60096012.
20 Y. D. Milusheva, R. I. Boukoureshtlieva, S. M. Hristov and
A. R. Kaisheva, Bulg. Chem. Commun., 2011, 43, 4247.
21 Y. Lv, M. Liu, Y. Xu, D. Cao and J. Feng, J. Power Sources,
2013, 225, 124128.
22 R. Balasubramanian, A. Veluchamy, N. Venkatakrishnan and
R. Gangadharan, J. Power Sources, 1995, 56, 197199.
23 M. G. Medeiros and E. G. Dow, J. Power Sources, 1999, 80,
7882.
24 J. L. Murray, ASM Handbook Volume 3: Alloy Phase Diagrams,
ASM International, 1998.
25 J. Chen and F. Y. Cheng, Acc. Chem. Res., 2009, 42, 713723.
26 C. Burda, X. Chen, R. Narayanan and M. A. El-Sayed, Chem.
Rev., 2005, 105, 10251102.
27 L. Ji, Z. Lin, M. Alcoutlabi and X. Zhang, Energy Environ. Sci.,
2011, 4, 26822699.
28 Y. Bing, H. Liu, L. Zhang, D. Ghosh and J. Zhang, Chem. Soc.
Rev., 2010, 39, 21842202.
29 Y. Qiao and C. M. Li, J. Mater. Chem., 2011, 21, 40274036.
30 Y. S. Meng and M. E. Arroyo-de Dompablo, Energy Environ.
Sci., 2009, 2, 589609.
31 G. Ceder, G. Hautier, A. Jain and S. P. Ong, MRS Bull., 2011,
36, 185191.
32 D. Shin and C. Wolverton, Scr. Mater., 2010, 63, 680685.
33 R. W. P. Wagemans, J. H. van Lenthe, P. E. de Jongh, A. J. van
Dillen and K. P. de Jong, J. Am. Chem. Soc., 2005, 127, 16675
16680.
34 B. W. Jensen, M. Gaadingwe, D. R. Macfarlane and
M. Forsyth, Electrochim. Acta, 2008, 53, 58815884.
35 H. P. Godard, W. P. Jepson, M. R. Bothwell and R. L. Lane,
The Corrosion of Light Metals, John Wiley & Sons, 1967.
36 S. Sathyanarayana and N. Munichandraiah, J. Appl.
Electrochem., 1981, 11, 3339.
37 T. Khoo, P. C. Howlett, M. Tsagouria, D. R. MacFarlane and
M. Forsyth, Electrochim. Acta, 2011, 58, 583588.
Mater. Horiz., 2014, 1, 196206 | 205

Materials Horizons
38 A. Morozan, B. Jousselme and S. Palacin, Energy Environ. Sci.,
2011, 4, 12381254.
39 F. Y. Cheng, J. Shen, B. Peng, Y. D. Pan, Z. L. Tao and J. Chen,
Nat. Chem., 2011, 3, 7984.
40 J. Perez, E. R. Gonzalez and E. A. Ticianelli, Electrochim. Acta,
1998, 44, 13291339.
41 L. Genies, R. Faure and R. Durand, Electrochim. Acta, 1998,
44, 13171327.
42 J. Greeley, I. E. L. Stephens, A. S. Bondarenko, T. P. Johansson,
H. A. Hansen, T. F. Jaramillo, J. Rossmeisl, I. Chorkendor
and J. K. Nrskov, Nat. Chem., 2009, 1, 552556.
43 I. E. L. Stephens, A. S. Bondarenko, U. Gronbjerg,
J. Rossmeisl and I. Chorkendor, Energy Environ. Sci.,
2012, 5, 67446762.
Published on 10 September 2013. Downloaded on 12/12/2014 21:07:04.
44 J. R. Kitchin, J. K. Norskov, M. A. Barteau and J. G. Chen,
J. Chem. Phys., 2004, 120, 1024010246.
45 F. H. B. Lima, J. R. C. Salgado, E. R. Gonzalez and
E. A. Ticianelli, J. Electrochem. Soc., 2007, 154, A369A375.
46 D. Wang, Y. Yu, H. L. Xin, R. Hovden, P. Ercius, J. A. Mundy,
H. Chen, J. H. Richard, D. A. Muller, F. J. DiSalvo and
H. D. Abruna, Nano Lett., 2012, 12, 52305238.
47 D. Wang, H. L. Xin, R. Hovden, H. Wang, Y. Yu, D. A. Muller,
F. J. DiSalvo and H. D. Abruna, Nat. Mater., 2013, 12, 8187.
48 H. Chen, D. Wang, Y. Yu, K. A. Newton, D. A. Muller,
H. Abruna and F. J. DiSalvo, J. Am. Chem. Soc., 2012, 134,
1845318459.
49 F. H. B. Lima and E. A. Ticianelli, Electrochim. Acta, 2004, 49,
40914099.
50 M. Oezaslan, F. Hasche and P. Strasser, J. Electrochem. Soc.,
2012, 159, B444B454.
51 L. H. Jiang, A. Hsu, D. Chu and R. R. Chen, J. Electroanal.
Chem., 2009, 629, 8793.
52 Y. F. Yang, Y. H. Zhou and C. S. Cha, Electrochim. Acta, 1995,
40, 25792586.
53 L. Jiang, A. Hsu, D. Chu and R. Chen, Electrochim. Acta, 2010,
55, 45064511.
54 T. J. Schmidt, V. Stamenkovic, M. Arenz, N. M. Markovic and
P. N. Ross, Electrochim. Acta, 2002, 47, 37653776.
55 B. Li and J. Prakash, Electrochem. Commun., 2009, 11, 1162
1165.
56 M. C. Oliveira, R. Rego, L. S. Fernandes and P. B. Tavares,
J. Power Sources, 2011, 196, 60926098.
57 D. A. Slanac, W. G. Hardin, K. P. Johnston and
K. J. Stevenson, J. Am. Chem. Soc., 2012, 134, 98129819.
58 D. S. Yang, D. Bhattacharjya, S. Inamdar, J. Park and J. S. Yu,
J. Am. Chem. Soc., 2012, 134, 1612716130.
59 W. Yang, T. P. Fellinger and M. Antonietti, J. Am. Chem. Soc.,
2011, 133, 206209.
60 H. Wang, T. Maiyalagan and X. Wang, ACS Catal., 2012, 2,
781794.
61 K. Gong, F. Du, Z. Xia, M. Durstock and L. Dai, Science, 2009,
323, 760764.
62 D. S. Geng, Y. Chen, Y. G. Chen, Y. L. Li, R. Y. Li, X. L. Sun,
S. Y. Ye and S. Knights, Energy Environ. Sci., 2011, 4, 760764.
206 | Mater. Horiz., 2014, 1, 196206
View Article Online
Minireview
63 L. Lai, J. R. Potts, D. Zhan, L. Wang, C. K. Poh, C. Tang,
H. Gong, Z. Shen, J. Lin and R. S. Ruo, Energy Environ.
Sci., 2012, 5, 79367942.
64 F. Y. Cheng, Y. Su, J. Liang, Z. L. Tao and J. Chen, Chem.
Mater., 2010, 22, 898905.
65 Y. Gorlin and T. F. Jaramillo, J. Am. Chem. Soc., 2010, 132,
1361213614.
66 J. Suntivich, H. A. Gasteiger, N. Yabuuchi, H. Nakanishi,
J. B. Goodenough and Y. S. Horn, Nat. Chem., 2011, 3, 546
550.
67 Z. S. Wu, S. B. Yang, Y. Sun, K. Parvez, X. L. Feng and
K. Mullen, J. Am. Chem. Soc., 2012, 134, 90829085.
68 Y. Y. Liang, Y. G. Li, H. L. Wang, J. G. Zhou, J. Wang,
T. Regier and H. J. Dai, Nat. Mater., 2011, 10, 780786.
69 Y. Liang, H. Wang, J. Zhou, Y. Li, J. Wang, T. Regier and
H. Dai, J. Am. Chem. Soc., 2012, 134, 35173523.
70 R. L. Liu, C. von Malotki, L. Arnold, N. Koshino,
H. Higashimura, M. Baumgarten and K. Mullen, J. Am.
Chem. Soc., 2011, 133, 1037210375.
71 J. S. Guo, H. X. Li, H. He, D. Chu and R. R. Chen, J. Phys.
Chem. C, 2011, 115, 84948502.
72 J. K. Nrskov, J. Rossmeisl, A. Logadottir, L. Lindqvist,
J. R. Kitchin, T. Bligaard and H. Jonsson, J. Phys. Chem. B,
2004, 108, 1788617892.
73 J. S. Guo, A. Hsu, D. Chu and R. R. Chen, J. Phys. Chem. C,
2010, 114, 43244330.
74 D. A. Slanac, W. G. Hardin, K. P. Johnston and
K. J. Stevenson, J. Am. Chem. Soc., 2012, 134, 98129819.
75 L. T. Qu, Y. Liu, J. B. Baek and L. M. Dai, ACS Nano, 2010, 4,
13211326.
76 T. N. Lambert, D. J. Davis, W. Lu, S. J. Limmer, P. G. Kotula,
A. Thuli, M. Hungate, G. Ruan, Z. Jin and J. M. Tour, Chem.
Commun., 2012, 48, 79317933.
77 I. Roche and K. Scott, J. Appl. Electrochem., 2009, 39, 197204.
78 Q. Zhou, C. M. Li, J. Li, X. Cui and D. Gervasio, J. Phys. Chem.
C, 2007, 111, 1121611222.
79 M. Maja, C. Orecchia, M. Strano, P. Tosco and M. Vanni,
Electrochim. Acta, 2000, 46, 423432.
80 S. L. Gojkovic, S. Gupta and R. F. Savinell, J. Electrochem.
Soc., 1998, 145, 34933499.
81 H. Wu and W. Chen, J. Am. Chem. Soc., 2011, 133, 15236
15239.
82 GreenVolt conrms a 150% power increase in its new
magnesiumairsaltwater-fuel-cell -TM- without an
increase in size & weight, The Free Library, Business Wire
2001, http://www.thefreelibrary.com/GreenVolt+Conrms+
A+150%25+Power+Increase+In+Its+New.-a078823900.
83 MAGPOWER, http://www.magpower.pt/X/home.cgi.
84 Hybridized magnesium air fuel cell with NiZn battery or
electrochemical capacitor as the ideal energy source for USV
sensor payloads, Department of Defense, Navy, N04080,
2004, http://sbirsource.com/sbir/awards/6590-hybridized-
magnesium-air-fuel-cell-with-ni-zn-battery-or-electrochemical-
capacitor-as-the-ideal-energy-source-for-usv-sensor-payloads.
This journal is The Royal Society of Chemistry 2014