PROGRESS REPORT
Magnesium-Air Batteries
Current Progress on Rechargeable Magnesium–Air Battery
Chun-Sheng Li, Yan Sun,* Florian Gebert, and Shu-Lei Chou*
Rechargeable Mg–air batteries are a promising alternative to Li–air cells
owing to the safety, low price originating from the abundant resource on the
earth, and high theoretical volumetric density (3832 A h L−1 for Mg anode
vs 2062 A h L−1 for Li). Only a few works are related to the highly reversible
Mg–air batteries. The fundamental scientific difficulties hindering the rapid
development of secondary Mg–air cells are attributed to the poor thermody-
namics and kinetics properties mainly owing to the MgO or MgO2 insulating
film as the initial discharge product on air–breathing cathode, contributing
to the increase of a large overpotential and a high polarization. Very recently,
remarkable progress on rechargeable Mg–air batteries is trying to overcome
the major limitations in organic electrolytes via the combination of the
first–principle calculation and experimental study. Therefore, this progress
report highlights a comprehensive and concise survey of the major progress
in the history of secondary Mg–air batteries, and the detailed illustrations of
corresponding reaction mechanisms. The overview is devoted to open up a
new area for manipulating the nanostructures to control the ideal reaction
pathway in novel cell configuration and to fully understand the future Mg–air
battery with improved energy density and cycling ability.
1. Introduction
With increasingly serious problems from the worldwide
energy crisis for fossil fuels and the air pollutions, renewable
clean energy storage and conversion in rechargeable batteries
will be urgently needed in the coming decades.[1–5] Desirable
rechargeable batteries are electrochemical devices in stable elec-
trolytes that efficiently convert chemical energy into electrical
energy during discharge, and then convert electrical energy
into chemical energy during charging.[6–11] The key electrode
materials should satisfy three strict requirements[2,3,12–15]: (i) A
large voltage gap between anode and cathode potentials delivers
an effective discharge plateau, while the electrodes composed
of lightweight elements operate multiple electrons transferred
Prof. C.-S. Li, Prof. Y. Sun
College of Chemical Engineering
North China University of Science and Technology
Tangshan City, Hebei Province 063009, P. R. China
E-mail: juzi147@mail.nankai.edu.cn
F. Gebert, Dr. S.-L. Chou
Institute for Superconducting and Electronic Materials
University of Wollongong
Wollongong, NSW 2522, Australia
E-mail: shulei@uow.edu.au
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.201700869.
DOI: 10.1002/aenm.201700869
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in reversible oxidation/reduction reaction
to achieve a high energy density. (ii) Fast
charge transport and high exchanging
current density of materials dramatically
reduce the polarization and further pro-
vide a high power density. (iii) Uniform
micro/nanostructures are associated with
increased specific surfaces areas and
decreased ionic diffusion over distance
and time, resulting in a long lifetime and
a good cycling stability.
Among various energy sources in his-
tory, rechargeable cells are lead (Pb)–acid,
nickel–chromium (Ni–Cr), nickel–metal
hydride (Ni–MH), redox flow, lithium–
ion, fuel cells and metal–air batteries.[2]
In particular, rechargeable metal–air bat-
teries have received great interest due to
a huge theoretical specific energy density,
deriving from a unique cell structure. In
this system, only the metal (Li, Na, Mg,
Al, Zn, Si, Fe, Sn, etc.) anode is assem-
bled in the cell, while the active cathode
material is oxygen (O2), directly obtained
from the atmosphere.[12–17] Figure 1a presents a summary of
basic theoretical properties and electrochemical reactions in
typical metal–air batteries. For instance, rechargeable Li–air
batteries can provide a theoretical cell voltage of 2.96 V and a
theoretical specific energy density of 3.4 kW h kg−1. In this par-
ticular battery, the decomposition of lithium peroxide (Li2O2),
despite being an explosive and poisonous compound, plays a
vital role in the improved charge transport because it demon-
strates a highly reversible reaction between the discharge and
charge process.[18,19] The maximum specific capacity of sec-
ondary Li–air batteries reaches an initial discharge capacity
of 14000 mA h g−1 at a current density of 140 mA g−1, using
Co3O4/reduced graphene oxide nanocomposites as electrocata-
lysts.[20] Unfortunately, although they are the focus of numerous
investigations, lithium–air batteries are still accompanied by
the major drawbacks of the high price of metallic lithium (The
USD $160000–180000/ton as of May 2017) and safety issues in
an organic electrolyte.
Magnesium provides a number of improvements com-
pared to metallic Li, including its abundance in the earth’s
crust (2.08% for Mg vs 0.0065% for Li) and environmental
friendliness. Moreover, rechargeable Mg–O2 battery allows a
theoretical volumetric density and a specific energy density of
14 kW h L−1 and 3.9 kW h kg−1, respectively, assuming MgO
is formed as the discharge product.[21,22] These values are
much larger than those of Li–O2 cells on the basis of Li2O2
(8.0 kW h L−1 and 3.4 kW h kg−1). Though a great number
of efforts have focused on the widespread studies of Li–air
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Chunsheng Li received his

M.S. and Ph.D. degree from
the Institute of New Energy
Materials Chemistry in
Nankai University (Tianjin,
China) in 2007 and 2010,
respectively. He is currently a
Professor at the North China
University of Science and
Technology, Hebei Province,
since 2017. He is mainly
engaged in nanostructured
materials for the advanced applications in metal-air
batteries, such as Mg-air batteries, Zn-air batteries, and
Al-air batteries.

Yan Sun obtained her B.S.

degree from the Liaoning
Normal University in 2004,
M.S. degree from Wenzhou
University in 2007, and
Ph.D. degree from Nankai
University (China) in 2010.
She was promoted to a full
Professor in North China
University of Science and
Technology in 2017. She led
a research team interesting
on functional micro/nanomaterials and their clean energy
storage and conversion in metal-air batteries, lithium-ion
batteries, and sodium-ion batteries.

Shu-Lei Chou is a senior

research fellow in ISEM at
University of Wollongong
(UOW). He obtained his
Figure 1. a) A comparison of theoretical specific energy densities of Bachelor (1999) and
typical metal–air batteries as a function of prices of corresponding anode
Master degree (2004) in
metals. The energy densities are calculated values reported in the litera-
ture and include oxygen,[27–30] while the prices are obtained in May 2017 Nankai University, China.
from https://www.metalprices.com and http://www.shmet.com. b) Sche- His research has been
matic cell configurations of proposed secondary Mg−air cells with hybrid focused on energy storage
electrolytes, illustrating the development of electrochemical catalysts. materials for battery
applications, especially
on novel composite
batteries, only a few works address the highly reversible Mg–air materials, new binders, and new electrolytes for Li/Na
batteries.[21–25] The fundamental scientific difficulties hindering batteries.
the rapid development of secondary Mg–air cells in traditional
aqueous electrolytes are: (1) The poor thermodynamics and
kinetics properties of MgO or MgO2 films lead to a large polari-
zation and a highly irreversible capacity, which are formed the enhancement of energy conversion efficiency and high–rate
during the initial discharge process. Moreover, the MgO and stability in rechargeable Mg–air batteries. To overcome these
MgO2 as insulating products are electrochemically inert and issues, D. J. Siegel’s group investigated the chemical reaction
difficult to convert back into metallic Mg under moderate elec- pathways according to the thermodynamic parameters via
trochemical conditions. (2) The synergetic combination of the first–principle calculations, aiming to thoroughly understand
efficient electrocatalysts for 4e oxygen reduction reaction in an the free energy evolutions of secondary Mg–air batteries.[21,22]
air cathode, the novel organic electrolyte with a high ionic con- From the results, the MgO intermediate shows very low round-
ductivity, and micro/nanoscale Mg anode is urgent to facilitate trip efficiencies, associated with large overvoltage drops. With

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magnesium peroxide (MgO2) as the intermediate, however, the
Mg–air batteries might achieve a 90% round–trip efficiencies
and a low polarization.
Some outstanding reviews have been published in recent
years on primary Mg–air batteries,[16,26] covering the spec-
trum from principle studies to practical applications. Never-
theless, inspired by other secondary batteries, improvements
on rechargeable Mg–air batteries are sought to resolve the
remaining problems at the present time (Figure 1b). This
progress report offers a comprehensive and concise survey of
the major developments in the history of secondary Mg–air
batteries and detailed illustrations of corresponding reaction
mechanisms. The close relationships between the Mg anode,
organic electrolyte and air cathode with electrocatalysts for
oxygen reduction are also discussed. The report is intended to
pave the way for future study and improvements in the design
of novel cell configurations with excellent energy density and
enhanced cycling retention performance.
2. The Rapid Development of Rechargeable
Mg–Air Batteries
2.1. The History of Rechargeable Mg–Air Batteries
Based on a comprehensive survey, the development history of
Mg–air batteries can be divided into four steps as illustrated
in, Figure 2: the primary Mg–air battery, the rechargeable
Mg2Ni–air battery, the rechargeable Mg–air battery in an
organic electrolyte, and the future rechargeable Mg–air cells
with hybrid electrolytes.
2.2. The Recent Progress of Primary Mg–Air Batteries
The preliminary era of primary Mg–air batteries involved the
fundamental scientific challenges of novel Mg anodes with a
high electrochemical activity, a neutral electrolyte, and a bifunc-
tional air cathode. Table 1 summarizes the significant break-
throughs of primary Mg–air batteries in recent years. However,
in an aqueous electrolyte, Mg electrodes are not suitable for
Figure 2.  The history of rechargeable Mg–air batteries and its major developments.
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reversible air batteries due to the following reasons: (a) The
self-corrosion of Mg results in the formation of insulating
Mg(OH)2 product, passivating further anode reactions. (b) The
H2 gas production from parasitic reactions destroys the pres-
sure balance in the sealed cell space and dramatically increases
the cell polarization. (c) Superior electrocatalysts for oxygen
reduction with good electrocatalytic activity are needed for long
lifespans. As early as 1958, Hoey’s group first studied the cor-
rosion behavior of a polarized Mg anode in aqueous NaCl solu-
tion, proposing a plausible mechanism of Mg dissolution and a
hydrogen embrittlement theory of cathodic corrosion.[31] From
2006 to 2014, Chen and his colleagues found that Mg spheres,
plates, nanorods and sea urchin–like nanostructures were
successfully fabricated through a physical vapor deposition
process by modulating the flow–rates of Ar carrier gas.[32]
In these morphologies, the Mg sea urchin shape, composed
of numerous nanoneedles, exhibited a high anode current
density of 136 mA cm−2 and a reasonable power density of
565 W h kg−1, attributed to the porous micro/nanomaterials
with high chemical activity and low Mg polarization/cor-
rosion rate in Mg(NO3)2–NaNO2 aqueous electrolyte for a
high–rate discharge. He also reviewed the current status of
outstanding primary Mg–air batteries, focusing on the critical
role of Mg nanomaterials in advanced applications in high-
energy storage and reversible conversion.[16,26] Inspired by
these works, porous Mg thin films (100 nm in thickness) and
Mg–Al–Pb–Ce–Y alloys have been explored to improve the
anodic efficiency.[33–35]
For the electrolyte, much research of ionic liquids as useful
additives took place from 2011 to 2014 in order to obtain high
anode potentials and energy densities.[36–38] In addition, chi-
tosan−choline nitrate (CS−[Ch][NO3]) thin–film polymer elec-
trolytes have been found to deliver a high ionic conductivity of
8.9 × 10−3 S cm−1 and a volumetric power density of 3.9 W L−1
for Mg–air cells.[39] Reported in 2015, water soluble graphene in
NaCl solution displays a 1030.71 mA h g−1 discharge capacity,
which is advantageous in reducing the anodic self–discharge
rate.[40] In particular, McCloskey and Luntz reported that 0.5 m
NaNO3 allows 50% higher anode utilization by decreasing the
H2 corrosion and 60% higher discharge capacity than that of
0.5 m NaCl solution.[41]
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Table 1.  The important developments of primary Mg–air batteries during very recent years.

Materials Morphology Synthesizing method Discharge performance Literatures Published

year
Mg anode Mg–Al–Pb–Ce–Y alloy Mg sheets Electromagnetic Mg–Al–Pb–Ce–Y alloy provides 60.5±0.2% [35] 2016
induction anodic efficiency at 10 mA cm−2, better than
pure Mg, AZ31,a) Mg–Al–Pb, Mg–Al–Zn (AZ)
and Mg–Al–Mn (AM) alloys.
Mg–air bioelectric batteries Thin film Chemical deposition A discharge capacity of 3.79 mA h cm−2 at a [46] 2016
composed of silk fibroin– and polymerization current of 10 µA cm−2 and a specific energy
polypyrrole film density of 4.70 mW h cm−2.
Mg-Al-Pb and Mg-Al-Pb-In Sheets Electromagnetic Mg-Al-Pb-In anode delivers a power density [34] 2014
alloy induction of 94.5 mW cm−2.
Porous Mg thin films Mg films with 100 nm Magnetron Mg–air battery displays an open-circuit voltage [33] 2013
thickness sputtering of 1.41 V, a plateau of 0.8–1.0 V, and a specific
discharge capacity of 821 mA h g−1.
Mico/nano Mg structures Spheres, plates, nanorods and Physical vapor 565 W h kg−1 at 5 mA cm−2 for [32] 2006
seaurchin-like nanostructures deposition Mg seaurchin.
Electrolyte Mg anode corrosion Mg sheets — NaNO3 solution provides 50% higher Mg [41] 2016
oxidation faradaic efficiency and 60% larger
discharge capacity than that of NaCl electrolyte.
Water-soluble graphene as A flake-like structure Solution preparation 1030.71 mA h g−1 specific discharge capacity [40] 2015
electrolyte additive in of Mg–air battery.
NaCl solution
Chitosan−choline nitrate — A casting method The polymer electrolyte shows a high ionic [39] 2014
(CS−[Ch][NO3]) thin-film conductivity of 8.9 × 10−3 S cm−1 and a volu-
electrolytes metric power density of 3.9 W L−1 for the cell.
Ionic-liquid-based non- — Electrochemical A mechanism of EtMgBr is reported for Mg–air [38] 2014
aqueous electrolyte synthesis of EtMgBr cells with high energy density.
Grignard reagent
[P6,6,6,14][Cl] based ionic liquid — — [P6,6,6,14][Cl] based electrolyte obtains a [36,37] 2014, 2011
electrolyte high Mg potential (−1.6 V vs Ag|AgCl) and
a stable high current density.
Solid-state oxygen shuttle film — Mg–air batteries observed a higher open-circuit [43] 2015
metal-air battery of 1.81 V and Mg utilization of 52%.
Cathode SmMn2O5 electrocatalyst Nanoparticles Co–precipitation and Discharge 300 min at 1 mA cm−2 in [44] 2016
heat–treatment 1 m NaCl electrolyte.
Ultrafine Mn3O4 nanowires/ Electrocatalysts for air cathode Microwave 3D catalysts have an electron transfer number of [45] 2016
three–dimensional gra- irradiation 3.95 (at 0.60 V vs Ag/AgCl) and kinetic current
phene/single–walled carbon density of 21.7–28.8 mA cm−2. Mg/air batteries
nanotube composites demonstrate a high cell open circuit voltage
(1.49 V), a high plateau voltage (1.34 V), and
a long discharge time (4177 min) at 0.2 mA cm−1.
PTFE/carbon fiber felts Super–hydrophobic porous Template method 73.3 mW cm−2 with 30% regular pores at [42] 2015
gas diffusion layers current density of 125 mA cm−1.

a)The composition of the AZ31 magnesium alloy sheet is 96% Mg, 3% Al, and 1% Zn. Mg-Al-Pb alloy is Mg-6 wt% Al-5 wt% Pb. Mg-Al-Pb-In alloy is Mg-6 wt% Al-5 wt% Pb-1 wt% In.

For the air cathode, Miao and Liu stated that PTFE/carbon
fiber felts as super–hydrophobic gas diffusion layers contrib-
uted 30% regular pores for a fast O2 supply and rapid kinetic
reactions.[42] To diminish the negative effects of evaporation
and decomposition of the electrolyte, Inoishi’s group invented
a solid–state metal–air cell employing Ca–stabilized ZrO2 ion–
conducting shuttle as the electrolyte (Figure 3a).[43] Mg–air and
Li–air oxygen–shuttle batteries displayed a higher open-circuit
(OCV) of 1.81 V compared with other mildly reducing anodes
(Zn, Fe, Si, and Sn), resulting from the excellent electrochem-
ical activity of Li and Mg metals and the high electron/ionic
conductivity of the shuttle (Figure 3 b). However, the Mg–air
oxygen–shuttle cell is unsuited as a rechargeable system due
to the clear increase of O2 pressure in the anode chamber,
greatly increasing the electrode resistance even after the initial
discharge as shown in Figure 3 c–d. Recently, Wang and Yao
et al. reported in 2016 that a SmMn2O5 electrocatalyst exhib-
ited catalytic activity via a fast 4e transfer reaction and superior
stability in 1 m NaCl electrolyte for Mg–air battery, owing to the
Mn–O* bonding strength of p-d hybridization in the mullite
structure.[44] In addition, our previous work in 2016 described
that ultrafine Mn3O4 nanowires/three–dimensional graphene/
single–walled carbon nanotube (3D GN/SWCNT) composites
demonstrated an electron transfer number of 3.95 (at 0.60 V vs

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Figure 3.  Solid–state oxygen shuttle rechargeable metal–air battery: a) Schematic of the oxygen shuttle concept.b) First discharge curves for a selection
of metal–air batteries with various metals as anodes. Impedance plots of the metal–air oxygen shuttle battery before and after discharge: c) Zn–air cell,
and d) Mg–air cell. Reproduced with permission.[43] Copyright 2015, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ag/AgCl) and a kinetic current density of 21.7–28.8 mA cm−2
(52% of the Pt/C values) as illustrated in Figure 4, which were
synthesized by high–efficient microwave irradiation.[45] In our
work, the Mg–air batteries assembled from the 3D electrocata-
lysts demonstrate a high cell open circuit voltage (1.49 V), a high
plateau voltage (1.34 V), and a long operating life (4177 min) at
0.2 mA cm−1.
2.3. Metal Hydride–Air Battery
The second step was the development of a rechargeable
Mg2Ni–air battery. The metal hydride–air (MH–air) battery,
a new cell configuration, is the combination of the recharge-
able Ni–MH battery and the metal–air battery in the strongly
alkaline electrolyte.[27,47–54] As we know, Ni–MH secondary
batteries with low self–discharge properties, consisting of a
hydrogen storage alloy as the anode and Ni(OH)2 as the cathode
in KOH solution, have seen extensive application in cam-
eras, notebook computers, mobile phones, and hybrid electric
vehicles following their commercialization in 1990. The great
virtues of the Ni–MH power source are its safety during long
charge–discharge periods and its reliability at a moderate power
density. The electrochemical reactions during charge–discharge
cycles in the Ni–MH battery can be expressed as follows:
(−) MH + OH− ↔ M + H2O + e − (1)
(+) NiOOH + H2O + e − ↔ Ni (OH)2 + OH− (2)
Overall reaction : MH + NiOOH ↔ M + Ni (OH)2 (3)
However, the nominal capacity of the overall Ni–MH bat-
tery limited by the positive electrode, implying that most of the
cell volume in the sealed system is occupied by the Ni(OH)2
electrode. Thus, it is expedient to replace the heavy Ni(OH)2
cathode by a much lighter air–breathing cathode in order to sig-
nificantly raise the theoretical energy capacity of the cell. This
inspired the novel concept of the rechargeable metal hydride–
air battery. The actual mechanism occurred in the MH–air cell
is described in reactions 4 to 6, and the intermediate species of
Mg2NiH4 produced during the cycles.
(−) 4OH− ↔ O2 + 2H2O + 4e − (4)
(+) Mg 2Ni + 4H2O + 4e − ↔ Mg 2NiH4 + 4OH− (5)
Overall reaction : Mg 2Ni + 2H2O ↔ Mg 2NiH4 + O2 (6)
The rare–earth based AB5–type and Mg–based A2B–type
hydrogen–storage alloys, as representative anode materials for

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Figure 4.  a) Typical XRD patterns of (I) Sample 1, commercial 3D GN/SWCNT sandwiches, (II) Sample 2, Mn3O4 nanosquares/3D GN/SWCNT com-
posite, and (III) Sample 3, ultrafine Mn3O4 nanowires/3D GN/SWCNT composite. b–e) SEM and TEM/HRTEM images of Mn3O4 nanostructures/3D
GN/SWCNT: b) Commercial pure 3D GN/SWCNT sandwiches for Sample 1, c) Well–defined Mn3O4 nanowires/3D GN/SWCNT composite for Sample
3. Representative TEM/HRTEM images d–e) of a single–stranded Mn3O4 nanowire. f) Rotating–disk voltammograms of Mn3O4 nanowires/3D GN/
SWCNT composite (Sample 3) in O2–saturated 0.1 m KOH at a sweep rate of 10 mV s−1 and different rotation rates. g) Typical discharge curves of
the Mg–air batteries measured with a current density of 0.2 mA cm−2 for ultrafine Mn3O4 nanowires/3D GN/SWCNT composite in the electrolyte of
a mixed electrolyte of Mg(NO3)2 (2.6 m) and NaNO2 (3.6 m) with an additive of 1.0 wt% [P6,6,6,14][Cl] ionic liquid. Reproduced with permission.[45]
Copyright 2016, American Chemical Society.

reversible Ni–MH batteries, can be also used in MH–air bat-
teries. For instance, AB5–type hydrogen–storage alloys exhibit a
low hydrogen storage capacity (1.37 wt% by forming LaNi5H6),
an electrochemical equivalent of alloy (372 mA h g−1) and good
corrosion resistance. In the AB5 composition, the A stands
for the mixed elements of rare–earth metals from ore extrac-
tion, and the B is a complex component (including Ni, Co, Al,
Mn, Ce, Sn metals) to give a protective function for the stable
hydrogen storage efficiency. LaNi5–based alloys have been
reported as anodes in MH–air batteries in recent decades,[47–52]
but obvious problems should still be addressed for promising
applications, such as the high cost of rare–earth metals and
the relatively low hydrogen storage density of heavy elements.
To solve these critical issues, Mg2Ni, as one of the most impor-
tant A2B–type hydrogen–storage alloys, has been developed as
an attractive substitute for alloy anodes in MH–air batteries,
owing to the low cost of abundant Mg, a high hydrogen storage
capacity (3.61 wt% calculated from Mg2NiH4) and theoretical
gravimetric energy density (999 mA h g–1). For example, Arof
et al. reported polycrystalline Mg2Ni alloy powders fabricated
using a mechanical alloying strategy.[27] The MH–air battery
comprises a Mg2Ni anode (to be converted to Mg2NiH4), an air
cathode using manganese as an electrocatalyst and a 6 m KOH
electrolyte, as illustrated in Figure 5a. The study concluded that
the Mg2Ni alloy is helpful for improving open–circuit voltage
compared with the LaNi5–based alloys. In addition, the first dis-
charge–charge cycle of this MH–air battery activates the Mg2Ni
alloy, so that the discharge capacity gradually increases in the fol-
lowing two cycles (Figure 5 b). According to the phase and shape
evolutions before and after cycling, the degradation in capacity
over 62 cycles is mainly attributed to the oxidation of Mg2Ni,
which forms an insulating Mg(OH)2 film on the electrode/
electrolyte interface, seriously damaging the morphology of the
alloy anode and inhibits further cell reactions. This phenom-
enon was strongly supported by Wang HB et al. in 2009, who
found that a part of the Mg2NiH4 formed in reaction 5 spon-
taneously decomposes into Mg2Ni and H2 gas via the parasitic
reaction 7.[55] At the same time, the active Mg2Ni undergoes a
possible hydrolysis as written in reaction 8. Thus, the combined
self-corrosion reactions of Mg2NiH4 produce Mg(OH)2, metallic
Ni and H2 gas as indicated in reaction 9. From the viewpoint
of thermodynamic theory, the hydrolysis of Mg2NiH4 is much
easier than that of Mg2Ni, since ΔGfθMg2NiH4 (–64.4 kJ mol−1) <
ΔGfθMg2Ni (–51.9 kJ mol−1). Additionally, the bifunctional air elec-
trodes are easily destroyed at the charging stage.[52] Therefore,
practical rechargeable Mg2Ni–air batteries for implementation
in portable devices, assuming an acceptable high energy den-
sity, should satisfy several strict requirements: (i) Mg2Ni micro/
nanostructures, which generally govern the hydrogen diffusion
rate from the active surface to the interior of MH electrode, and
tend to balance the anode expansion during hydriding/dehy-
driding process, (ii) an electrolyte with a low self–discharge
rate or alloy corrosion, and (iii) powerful electrocatalysts for the
oxygen reduction reaction to realize high–rate capabilities.

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Figure 5.  a) Cross-sectional view of an MH–air battery and its components. b) Charge–discharge curves of a Mg2Ni|6 m KOH|O2 battery. The inset in
b) is the scanning electron micrographs of Mg2Ni–graphite–PVA anode after cycling. Reproduced with permission.[27] Copyright 2003, Elsevier.
The self-corrosion reactions of Mg2NiH4 are given as:
(1st step ) : Mg 2NiH4 (s) → Mg 2Ni (s) + 2H2 (g ) (7)
(2nd step ) : Mg 2Ni (s) + 4H2O ( l ) → 2Mg (OH)2 (s) (8)
+ Ni + 2H2 ( g )
(Overall reaction ) : Mg 2NiH4 (s) + 4H2O ( l ) → 2Mg (OH)2 (s)
(9)
+ Ni + 4H2 ( g )
2.4. Rechargeable Mg-O2 Battery
Rechargeable metal–air batteries for alternative energy storage
technologies are considered a top priority to reduce the con-
sumption of fossil fuels and minimize air pollution. Among
these technologies, the secondary Li–O2 battery has achieved
particular attention in recent years because it provides fasci-
nating theoretical performances.[12,15,18–20] However, a major
problem still remains in Li–O2 cells in that a large quantity
of hazardous Li2O2 is deposited on the air cathode during
discharging, which decomposes at high charging potentials
(3.1 V vs Li+/Li). More importantly, Li2O2, as a highly explo-
sive material, is too dangerous for the safety demands of prac-
tical commercial applications. Fortunately, the rechargeable
Mg–air battery demonstrates an outstanding theoretical volu-
metric density of 14 kW h L−1 and a superior theoretical energy
capacity of 3.9 kW h kg−1, exceeding the corresponding theo-
retical data of Li–O2 cells. In the organic electrolyte, the MgO
that is precipitated upon discharging is environmentally benign
but does not easily react further even at high charging voltages.
Therefore, high–efficiency catalysts to increase the reactivity of
MgO during charging in suitable nonaqueous electrolytes are
urgently needed for the scientific exploitation of this battery.
The discharge products are vital for secondary metal–O2
cells since the reaction pathways associating the chemical
reactions depend on them. In the primary Mg–O2 battery,
Mg(OH)2 is combined with Mg2+ ions in the aqueous electro-
lyte and OH– is reduced using O2 in porous cathodes upon
discharge. The overall reaction can be expressed as follows:
2Mg + O2 + 2H2O → 2Mg(OH)2. The standard Gibbs free
energy of Mg(OH)2 (ΔGfθ −833.7 kJ mol−1) establishes a high
energy barrier, leading to the Mg anode being operated as an
irreversible electrode in aqueous solution. In nonaqueous
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electrolyte, when Mg–O2 cells discharge, O2 is catalytically
reduced to O2– at the bifunctional air cathode to generate solid
MgO2 and MgO. The ΔGfθ of MgO and MgO2 are –568.9 and
–567.8 kJ mol−1, respectively. The Gibbs free energy for the
decomposition of MgO2 is slightly lower than that of MgO
on the cathode surface. Interestingly, a similar phenomenon
is observed in rechargeable Li–O2 and Na–O2 batteries, and
it is clear that Li2O2 and Na2O2 with low Gibbs free energy
barriers undergo an efficiently reversible complexation and
decomposition, in good agreement with the reported refer-
ences.[12–15,18–20] Thus, we make a prediction that it is a more
formidable challenge to develop a rechargeable Al–O2 battery,
because both Al2O3 (ΔGfθ: –1582.3 kJ mol−1) and Al(OH)3 (ΔGfθ:
–1306.0 kJ mol−1) present very large obstacles based on ther-
modynamic energy data.[56] For the reasons mentioned above,
passive Al(OH)3 film always suffers from the poor interfacial
kinetics of further dissolution of the Al anode.[29] These types of
analyses will greatly deepen our understanding of the thermo-
dynamics and kinetics of rechargeable metal–O2 batteries.
To oxidize MgO precipitate, Shiga et al. established a catalytic
cycle for novel rechargeable Mg–air batteries, utilizing the iodine
(I2)–dimethylsulfoxide (DMSO)[23] and the 2,2,6,6–tetramethylpi-
peridine-oxyl (TEMPO)−anion complexes[24] as electrocatalysts
for air cathodes in 2013–2014 (Figure 6). MgO is easily pre-
pared by combining Mg2+ and reduced oxygen in nonaqueous
solution at room temperature (Mg2+ + 1/2O2 + 2e− → MgO).
During discharge, MgO is deposited on the O2−cathode/elec-
trolyte interface, and greatly diminishes the current density of
the electrocatalytic layer. However, MgO is very hard to reduce
to metallic Mg by cell charging, as shown by its high Gibbs free
energy of MgO (– 568.9 kJ mol−1), signifying high thermody-
namic stability. However, the I2–DMSO complex has the ability
to catalyze the oxidization of MgO. Experimental results con-
firmed that the concentration of dissolved Mg ions originating
from MgO rises proportionally to increased concentrations of
I2, corresponding to the reaction kinetics point of view. The
proposed reaction pathway can be written as: MgO + I2 + 2e− →
Mg2+ + 2I− + 1/2O2. The charging mechanism via catalyzed
oxidization of MgO is proposed in Figure 6a. First, MgI2
obtained from cathodic discharge is reduced to I2 by charging,
after which I2 reacts with DMSO to produce I2–DMSO to fur-
ther oxidize MgO precipitate into a Mg2+ ion and O2 gas. Sub-
sequently, the catalyzing cycle continuously repeats until the
MgO disappears from the cathode surface, reflecting the 2.0 V
© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Figure 6.  a) A proposed catalytic mechanism employing I2–DMSO for the charging process. b) Discharge–charge curves of the non-aqueous Mg–O2
battery with iodine at 60 °C. The black, pink, green, and red lines correspond to the first, second, third and fourth cycles, respectively. The blue line
represents a discharging–charging profile in the absence of iodine. Reproduced with permission.[23] Copyright 2013, The Royal Society of Chemistry.
c) Catalytic cycle for the TEMPO−anion complex during decomposition of metal oxide compounds, MxOy. The inset photographs show TEMPO+ClO4−
(upper) and TEMPO (lower). d) Cyclic performance of a nonaqueous Mg−O2 battery incorporating PTMA in the cathode at 60°C. Reproduced with
permission.[24] Copyright 2014, American Chemical Society.

charge plateau curve. The Mg–O2 battery provides a discharge
capacity of 2131 mA h g−1-cathode and a reversible capacity of
1590 mA h g−1 during the initial cycling at 60°C (Figure 6b).
Similarly, the TEMPO–anion complex (PTMA+ClO4–) also
electrochemically catalyzes the oxidization of MgO to enable
secondary Mg–O2 batteries via an analogous mechanism
(Figure 6c). At the charging stage, TEMPO reacts with an anion
to generate a TEMPO–anion complex. The complex immedi-
ately dissolves the solid MgO, and the TEMPO is regenerated.
TEMPO+X– can subsequently be recycled by associating the
regenerated TEMPO and another anion during cell charging.
Note that the TEMPO redox couple serves as a bridge for MgO
oxidization. As shown in Figure 6d, the potential profiles of
nonaqueous Mg–O2 battery demonstrate an initial discharging
capacity of 737 mA h g–1 and corresponding charge capacity
of 460 mA h g–1. The charging capacity was determined by
the dissolution of MgO via a catalytic process and the compl-
exation of PTMA+ClO4–. The irreversible capacity underwent
serious fading after the second cycle, attributed to the residual
MgO and the degeneration of the PTMA electrocatalyst in the
cathode. Nevertheless, these studies, exploiting the catalytic
capability of the complex in an air cathode, open up a new
route to design rechargeable Mg–O2 batteries.
Generally, the catalyzing efficiency of cell intermediates in
the liquid phase is greatly depended on the nature of electro-
lyte solvents. In lithium–air batteries, Huang and Shen’s group
developed an effective method to catalyze the discharge product
Li2O2, using I2 as a redox mediator in the electrolyte solvent of
n-butanol (BuOH).[57] The reaction kinetics for the dissolution
Li2O2 in the novel I2–BuOH electrolyte was 70 times faster than
that of I2–DMSO for the solvation of Li2O2. The Li2O2 depos-
ited on cathode surface is thoroughly disappeared below 3.6 V
(vs lithiated graphite electrode) during cell charging, which is
mainly influent by the reactive selectivity of BuOH with strong
hydrogen bonds. The idea could help to further pursue the
pathway to significantly enhance the cycling ability of sec-
ondary Mg–O2 cells.
The discharge species and reaction mechanism of the recharge-
able Mg–O2 battery, obtained from both experimental investiga-
tions and theoretical simulation, were reported by Siegel et al.
Figure 7a illustrates the half–reaction potentials for representa-
tive alkali metal–O2 cells. In Figure 7a line I–IV, the open–circuit
potentials (OCP) of these metal–O2 cells are based on the theoret-
ical potential voltage, mainly derived from negative half–reactions
of the active metal anode (Li, Na, K, and Mg) with O2 (dissolved
in tetrahydrofuran (THF)–based electrolyte) to form MxOy com-
pounds. Nevertheless, they are highly similar to the half–reac-
tion potentials involving superoxide formation (O2 + e– ↔ O2–).
In particular, in the Mg–O2 battery, the superoxide (O2–) reaction
(Figure 7a line V) processes a 0.9 V lower potential gap compared
with the direct formation of MgO (Figure 7a line IV). It is there-
fore essential to identify a plausible reaction mechanism based
on the thermodynamics. The phenomenon can be explained by
the “electrochemical–chemical–chemical” mechanism, which is
reported in the literature on Li–O2 batteries:[21,58–60] O2–, formed
by a one–electron oxygen reduction reaction, appears in the

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Figure 7.  The investigation of reaction pathway for a secondary Mg–O2 battery: a) Cell potentials and half-reaction potentials for several metal–O2
battery chemistries. The dashed red line corresponds to the potential at which O2 reduces to superoxide. b) Discharge/recharge cycles for a room-
temperature Mg–O2 cell at 5 µA cm−2 (superficial). Curves are labeled with the corresponding cycle numbers. Reproduced with permission.[21] Copyright
2015, American Chemical Society. c) Calculated free energy diagram for discharge and charging of a Mg–O2 cell using first-principles calculations,
for single-step reactions occurring on the oxygen rich MgO2 (111) “Orich-1” (black curve) and MgO2 (100) “Orich-3” (blue curve) surfaces. Energies
are plotted assuming the application of a potential, U, equal to the theoretical cell potential, U = U0. Reproduced with permission.[22] Copyright 2015,
American Chemical Society.

initial discharge step. MgO2 is formed by the reaction of Mg2+
ion and O2–, after which it decomposes into MgO and O2.[21,61]
Figure 7b exhibits the initial three cycles of a secondary Mg–O2
battery, using phenylmagnesium chloride:aluminum phenoxide
((PhMgCl)4−Al(OPh)3) in THF as the electrolyte. The discharge/
charge capacity and the coulombic efficiency of the initial cycle
are relatively low, presumably as a result of the low solubility and
mass transport of dissolved O2 in THF solvent.[21] The O2 perme-
ation through the nonaqueous electrolyte determines the overall
cell capacity at a high rate. Based on a series ex−situ characteriza-
tions (SEM, EDS, AES, XRD, and RS), the discharge product is
composed of 30% amorphous MgO2 and 70% MgO by volume.
More importantly, MgO2 preferentially decomposes during cell
charging due to the fast kinetics and favorable thermodynamics
(MgO2 ΔGfθ –567.8 kJ mol−1 vs MgO ΔGfθ –568.9 kJ mol−1).
Using first–principle calculations, Siegel et al. also studied the
diverse reaction mechanisms related to the two discharging prod-
ucts, MgO and MgO2. MgO2 as an intermediate is recommended,
rather than MgO, to decrease the overvoltages and dramatically
elevate the round–trip efficiencies to near 90% (Figure 7c). The
simulation results are in exact agreement with the above experi-
mental data. Therefore, research should aim to reveal the super-
oxide–controlled discharging mechanism for secondary Mg–O2
cells,[62,63] encouraging extensive efforts to design novel high–effi-
cient stable catalysts.
3. Conclusion and Outlook
This progress report is devoted to summarizing the development
history and current progress of rechargeable Mg–air batteries.
The rechargeable Mg–air battery, as one of the outstanding
candidates for the next generation of renewable power sources,
has been the focus of intensive research. In fact, its volumetric
density surpasses the value of Li–air batteries. However, only a
few reports have been released on the fundamental research on
secondary Mg–air cells in the last four years, even though pri-
mary Mg–air batteries have triggered widespread interest in Mg
micro/nanostructures and electrocatalysis in aqueous solution.
The most significant breakthroughs towards the secondary bat-
teries can be divided into two categories: first, I2–DMSO and
TEMPO−anion complexes in air-breathing cathodes are able
to catalytically decompose MgO precipitate into Mg2+ ions and
reduced oxygen during cell charging. The cells achieve a high
initial discharge capacity (737−2131 mA h g–1), but the irrevers-
ible capacities undergo serious fading upon cycling, which is
associated with the residual MgO on the cathode surface and
the degeneration of partial complex electrocatalysts. These com-
plex redox couples serve as a bridge to successfully manipulate
the cycle process in nonaqueous multivalent Mg−O2 systems.
For another, based on the combination of first–principles calcu-
lations and experimental study, the MgO2–controlled reaction

Adv. Energy Mater. 2017, 1700869 1700869  (9 of 11) © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
mechanism of rechargeable Mg–O2 battery is preferred, as this
pathway may decrease the thermodynamic overvoltages and
dramatically elevate the round–trip efficiencies to near 90%.
Although certain literature exists addressing the reaction
pathway and the catalytic cycle properties in secondary Mg–air
cells, many themes in the field still remain. Some significant
topics for future investigations are:
1. Previous studies illustrated in the progress report demon-
strate complex electrocatalysts for decomposing MgO during
the discharging stage; however, the sluggish kinetic efficien-
cy must also be urgently improved, because residual MgO on
the cathode after complete charging favors large cell polari­
zation and overvoltage, leading to reversible capacity fade
and poor cyclability. A sufficiently stable catalyst for revers-
ible formation–decomposition of MgO2 and MgO is required
to achieve long lifetimes. For instance, the nanocomposite
of graphene/Mn-based oxides/organic complex sustainably
operates as a functional catalyst for highly reversible charge/
discharge at a high current density.
2. In nonaqueous electrolyte, solubility and ionic transporta-
tion of O2 in organic solvent (such as THF) are critical for the
overall capacity and high–rate retention of secondary Mg–air
cells.[21,22,62–65] To better accommodate the active catalysts, a
novel electrolyte system with better solubility and fast diffusiv-
ity will be helpful. Figure 1b shows a schematic cell configura-
tion of future secondary Mg−air cells with a hybrid electrolyte.
From the figure, a nonaqueous solution as an electrolyte is
applied for highly active micro/nanoscale Mg with low polari-
zation and corrosion, and an aqueous solution as the catholyte
helps avoid the formation of insulating MgO and MgO2 films,
coupled with fast mass transport and high solubility of O2.
3. In secondary Mg–air batteries, only the Mg anode is sealed
within the cell, while O2 as the active cathode material is con-
tinuously breathed from the air. Thus, the nominal capacity
of the practical battery system is limited by the negative elec-
trode. Mg micro/nanomaterials with uniform shapes have
been shown to enhance the anode efficiency and the energy
density. Therefore, the close relationships between micro/na-
noscale Mg structures (e.g., phase, composition, morphology,
growth direction, and specific surface area) and the corre-
sponding reversible discharging/charging properties should
also be examined in detail in secondary Mg-air batteries.
4. In situ SEM, XRD, HRTEM, Raman measurements are
needed to monitor the microstructure variations (including
crystallographic lattice parameter changes, shapes, migra-
tion pathways of Mg2+, valence values) in order to further
elucidate the storage mechanisms in secondary Mg–air cells
during cycling. These in–situ analyses will facilitate the rapid
design of novel cell configurations, where multivalent metal-
air cells can produce excellent power energy output.
Acknowledgements
This work was fully supported by funding from the National Natural
Science Foundation of China (No. 21203051, 21643005), the Training
Program Foundation for the Excellent Youth Talents of Hebei Province,
Science Foundation for The Excellent Youth Scholars of Hebei
Adv. Energy Mater. 2017, 1700869 1700869  (10 of 11)
www.advenergymat.de
Province (B2017209250), and the Doctoral Foundation of North China
University of Science and Technology (GP201310). The work is also
supported by the Australian Research Council through a Linkage Project
(LP120200432). The authors also acknowledge Dr. Tania Silver for
scientific discussions and critical reading of the manuscript.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
air cathode, electrolyte, Mg anode, rechargeable magnesium–air batteries
Received: March 30, 2017
Revised: May 4, 2017
Published online:
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