Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.

View Article Online / Journal Homepage / Table of Contents for this issue

Featuring work from the group of Professor Jun Chen As featured in:
at Key Laboratory of Advanced Energy Materials
Chemistry (Ministry of Education), Chemistry College,
Nankai University, Tianjin, China.
Metal–air batteries: from oxygen reduction electrochemistry
to cathode catalysts

Metal–air batteries represent one class of promising power sources

for applications. The most prominent feature of a metal–air battery
is the combination of a metal anode with high energy density
(from the earth) and an air electrode with open structure to draw
cathode active materials (i.e., oxygen) from air. Four groups of
catalysts for the cathode oxygen reduction/evolution, the design See Cheng and Chen
Chem. Soc. Rev., 2012, 41, 2172.
& optimization of air-electrode structure, and the challenges and
perspectives of research directions are selectively surveyed.

www.rsc.org/chemsocrev
Registered Charity Number 207890
 Chem Soc Rev Dynamic Article Links
View Article Online

Cite this: Chem. Soc. Rev., 2012, 41, 2172–2192

www.rsc.org/csr CRITICAL REVIEW

Metal–air batteries: from oxygen reduction electrochemistry to
cathode catalysts
Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.

Fangyi Cheng and Jun Chen*

Received 27th August 2011
DOI: 10.1039/c1cs15228a

Because of the remarkably high theoretical energy output, metal–air batteries represent one class
of promising power sources for applications in next-generation electronics, electrified
transportation and energy storage of smart grids. The most prominent feature of a metal–air
battery is the combination of a metal anode with high energy density and an air electrode with
open structure to draw cathode active materials (i.e., oxygen) from air. In this critical review, we
present the fundamentals and recent advances related to the fields of metal–air batteries, with a
focus on the electrochemistry and materials chemistry of air electrodes. The battery
electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis
of aqueous and organic electrolytes. Four groups of extensively studied catalysts for the cathode
oxygen reduction/evolution are selectively surveyed from materials chemistry to electrode properties
and battery application: Pt and Pt-based alloys (e.g., PtAu nanoparticles), carbonaceous materials
(e.g., graphene nanosheets), transition-metal oxides (e.g., Mn-based spinels and perovskites), and
inorganic–organic composites (e.g., metal macrocycle derivatives). The design and optimization of
air-electrode structure are also outlined. Furthermore, remarks on the challenges and perspectives of
research directions are proposed for further development of metal–air batteries (219 references).

1. Introduction the worldwide consciousness of the low-carbon economy and

Modern society depends on the widespread use of reliable devices
for electrochemical energy storage and conversion. Nowadays,
Key Laboratory of Advanced Energy Materials Chemistry (Ministry
of Education), Chemistry College, Nankai University, Tianjin,
300071, People’s Republic of China. E-mail: chenabc@nankai.edu.cn;
Fax: +86-22-23506808; Tel: +86-22-23506808
sustainable concept greatly promote the progress of chemical
power sources such as batteries and fuel cells.1 Current prevailing
battery chemistries, rechargeable Li batteries in particular,
have gained commercial success in powering portable consumer
devices.2 However, they are still insufficient to keep pace with the
rapid development of electronics implementing 3-Generation
(3G) or 4G multimedia and communication technologies.

Fangyi Cheng received his Jun Chen is a Cheung Kong

BSc degree in Chemistry in Scholar Professor at Nankai
2003 and a PhD (with Prof. University. He is the director
Jun Chen) in Materials of the Key Laboratory of
Physics and Chemistry in Advanced Energy Materials
2009. At present, Dr Cheng Chemistry (Ministry of
is a lecturer at Nankai Uni- Education). He obtained his
versity. Since 2003, he has BSc and MSc degrees from
mainly studied the preparation Nankai University in 1989
of Mn-based oxides with and 1992, respectively, and
controllable structures and their his PhD from Wollongong
applications as battery materials University (Australia) in
or electrocatalysts. His current 1999. He held the NEDO
research interest is focused on fellowship at National Insti-
Fangyi Cheng functional materials for efficient Jun Chen tute of AIST Kansai Center
energy storage and conversion. (Japan) from 1999 to 2002.
His research expertise is nanomaterials for energy storage &
conversion with batteries, fuel cells, and solar cells.

2172 Chem. Soc. Rev., 2012, 41, 2172–2192 This journal is c The Royal Society of Chemistry 2012

In addition, the emerging applications of batteries in electrified
transportation (such as plug-in hybrid electric vehicles and
electric vehicles) and energy storage (for integrating renewable
energy in the so-called smart/intelligent grids) demand high
energy density, low cost, increased safety, and environmental
compatibility.3,4 Thus, an innovation in battery science and
technology is required to build better power sources for our
modern lifestyle needs.5 One of the main fields being explored for
the possible breakthrough refers to metal–air batteries.
Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
Metal–air batteries generate electricity through a redox
reaction between metal and oxygen in air. They are featured
with open cell structure, which admits the supply of the cathode
active material—oxygen—continuously and almost infinitely
from an external source (air). This feature makes them akin
to a fuel cell, with the ‘‘fuel’’ being a metal. Compared with
other ubiquitous batteries such as the primary Zn–MnO2
(Zn–Mn) and the rechargeable lead–acid, nickel–metal hydride
(Ni–MH) and lithium-ion batteries,6 the metal–air family has
notably higher theoretical energy density (Fig. 1). Such high
energy content is due to the fact that the cathode oxygen is not
stored in the cell and meanwhile the anode metal possesses a
high ratio of valence electrons to atomic nuclei.7 Especially, the
Li–air system releases an extremely high theoretical specific
energy of nearly 11 700 W h kg 1, which is close to the value for
one of the most energy-dense liquids—gasoline.8,9
In terms of theoretical gravimetric energy density, metal–air
batteries and fuel cells are possible contenders that could bring
electric propulsion on par with the current gasoline-engine
system. Fuel cells are viewed as a future solution to energy
issues due to advantages of environmental friendliness, high
energy conversion efficiency, rapid start-up and shut-down,
etc. However, fuel cell technologies are currently confronted
with formidable challenges ranging from difficult hydrogen
production/storage/transportation to complicated cell design,
low stability of the electrodes, and high cost of the materials.10–13
In comparison, light elements such as Zn, Al and Mg are well
known for their high abundance (e.g., Al is the most abundant
metal in the earth’s crust), low cost and environmental compat-
ibility. It is estimated that 21 months of global zinc production
Fig. 1 Comparison of the gravimetric energy density of some
representative types of primary/rechargeable batteries, metal–air batteries,
H2–air fuel cell and gasoline. The theoretical values are calculated on the
basis of thermodynamics of active materials.
This journal is c The Royal Society of Chemistry 2012
View Article Online
would sustain the production of 1 billion 10 kW h zinc–air
batteries to power all worldwide vehicles.14 In addition, the
anode design and the cathode catalyst in metal–air batteries are
less demanding as compared to fuel cells. Therefore, metal–air
chemistries hold promise for large-scale development and appli-
cations and have attracted increasing research interest because
of their prominent advantages.15
Of different types of metal–air chemistries, the primary
Zn–air cell has been commercialized as a hearing-aid battery;
Al–air and Mg–air cells have also found military applications
(e.g., underwater propulsion) and are under development as
saline systems.6 Although not fully electrically rechargeable at
present, Zn–air, Al–air and Mg–air batteries may be recharged
mechanically by quickly and simply replacing the discharged
anode and spent electrolyte slurry with fresh metal electrode
and electrolyte, making them ‘‘refuellable’’. In addition, the
spent electrolyte slurry containing metal oxides and oxide
hydroxides can be recycled and regenerated to the metallic form
using electrolysis or even solar thermal decomposition.14,16,17
Accordingly, these batteries can be indirectly rechargeable.
Electrically rechargeable metal–air batteries currently remain
at research and development level.9,15,18 Particularly, in 1996
Abraham and Jiang first reported a successful rechargeable
Li–O2 battery fabricated with a Li metal anode, a carbon
composite cathode, and a Li+ conductive organic polymer
electrolyte membrane.8 Later, Read investigated the effect of
electrolyte and air cathode formulation on the battery perfor-
mance of an aprotic Li–O2 cell.19 In 2006, Bruce and co-workers
demonstrated sustainable cycling of a Li–O2 battery for tens of
cycles.20 Recently, new research interest in Li–air batteries has
grown rapidly, aiming at taking the advantage of such a
fascinating system to substitute rechargeable Li–ion batteries
that are based on Li-intercalation electrodes.5,9,15,21
Like other battery technologies, metal–air batteries also
suffer from a series of scientific and technological problems.
The main issues include low utilization efficiency of the anode
and sluggish kinetics of the cathode, resulting in limited
practical energy density. For the anode, severe passivation
and corrosion of anode exist in electrolytes. The accumulation
of metal oxides, hydroxides or other species on the anode
surface retards further electrolyte access and thus prevents
discharging the remaining active material. The self-discharge
and corrosion of the metal anode degrades the coulombic
efficiency of the anode and shortens the battery shelf life. An
efficient strategy to address the deterioration issue is operating
the metal–air cells with reserve structure, in which one of the
key components of the cell is separated from a remainder until
activation.6 For the cathode (i.e., air electrode), the major
obstacles are the intrinsic slow reactions, high overpotentials,
and poor reversibility of oxygen chemistry.22 Reactions at the
cathode may involve complex processes and the underlying
mechanism remains elusive in many cases. Not surprisingly,
the air electrode is by far the dominating factor affecting the
performance of state-of-the-art metal–air batteries. While
using oxygen from surrounding air is generally considered as
the most intriguing aspect, the air electrode, unfortunately
appears to be the most complicated, expensive and sometimes
bulky component of a metal–air battery. As a result, if
metal–air batteries are to realize their full potential, the most
Chem. Soc. Rev., 2012, 41, 2172–2192 2173
 View Article Online

important tasks should include first elucidating the basic oxygen

chemistry and then exploiting highly efficient air electrodes for
accelerating the electrochemical oxygen reduction reaction
(ORR) and/or oxygen evolution reaction (OER). In this context,
much effort has been dedicated to the investigation of the
cathode reaction mechanism, the development of efficient bifunc-
tional catalytic materials for ORR/OER, and the rationalization
of electrode structures for facilitating mass/charge transport and
interface interaction.9,15,23–32
Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.

In this article, we intend to review the fundamentals and the

most recent and significant scientific progresses made in the
fields relevant to metal–air batteries, with emphasis placed on
air electrodes. The brief introduction of the operation principles,
the illustration of cathode electrochemical reactions, the survey
of intensively investigated catalyst materials, and the discussion
of the design and optimization of cathode structure will be
sequentially presented in the following sections, while the final
conclusion remarks on future challenges and perspectives. The
aim is to provide a better understanding of the promising
metal–air battery technologies.

2. Electrochemical cathode reactions

The metal–air battery is composed of a metal anode, an air-
electrode and a separator soaked in metal-ion conducting Fig. 2 Schematic representation of the structure and operation principle
electrolyte, as schematically shown in Fig. 2. In a basic of a metal–air battery and the liquid-gas-solid (catalyst) interface in the
chemistry, the metal anode is oxidized and releases electrons air electrode.
to the external circuit when the cell is discharged. At the same
time, oxygen diffuses into the cathode, accepts the electrons the anode reactions and overall reactions of different metal–air
from the anode and is reduced to oxygen-containing species. systems with alkaline aqueous electrolytes. It should be noted
The dissociated metal ions and oxygen-reduced species migrate that the actual cell potentials are generally much lower than
across the electrolyte and combine to form metal oxides. When the given theoretical values due to overpotentials derived from
the cell is charged (for rechargeable metal–air batteries), the both anode and cathode polarization.
process is reversed, with metal plating at the anode and oxygen The ORR in alkaline environments at ambient temperature
evolving at the cathode. Because the solubility of oxygen is is more favourable than in acidic environments because of
generally low in liquid electrolyte and a catalyst is required to better kinetics and lower overpotentials.22 The exchange current
facilitate its reduction, the cathode electrochemical reactions density is higher by approximately an order of magnitude,
mainly take place at the liquid–gas–solid interface (i.e., the rendering feasible the use of non-noble metal electrocatalysts.
so-called three-phase zone) in the air electrode. Consequently, Additionally, based on the Nernst equation, the electrode
oxygen transportation properties of the electrolyte play potential will nominally shift by 0.83 V ( 59 mV multiplied
important roles in determining the battery performance.26,27 by 14) if the pH value of electrolyte changes from 0 to 14. This
Furthermore, it should be noted that the involved electro- negative potential shift affects the electric field at electrode–
chemical reactions and the overall product may differ from electrolyte interface, resulting in significant weakening of binding
each other among various types of metal–air batteries, depending strengths for adsorbates, especially for charged species.30
on the specific metal, the electrolyte and the catalytic materials
adopted.24,25 In this section, the basic electrochemical cathode Table 1 Electrochemical reactions and the theoretical standard
potential of selected metal–air batteries with aqueous alkaline
reactions of metal–air batteries are discussed separately on the electrolytes
basis of aqueous and organic electrolytes.
Metal air cells Anode (a) and overall (o) reactions E0/Va
2.1 Aqueous electrolyte configuration
Zn–air (a) Zn + 2OH - ZnO + H2O + 2e 1.25
Metals such as Li, Mg, Al and Zn can react violently to (o) 2Zn + O2 - 2ZnO 1.65
Mg–air (a) 2Mg + 4OH - 2Mg(OH)2 + 4e 2.69
generate hydrogen in acidic media with a great deal of released
(o) 2Mg + O2 + 2H2O - 2Mg(OH)2 3.09
heat. The resulting severe anode corrosion and complicated Al–air (a) Al + 3OH - Al(OH)3 + 3e 2.31
thermal management make the acidic electrolyte inappropriate (o) 4Al + 3O2 + 6H2O - Al(OH)3 2.71
for practical application. In addition, there are few electro- Li–air (a) Li + OH - LiOH + e 2.95
(o) 4Li + O2 + 2H2O - 4LiOH 3.35
catalytic materials that are stable under the strongly acidic
circumstances and the aggressive oxidizing environments at
a
The standard potentials (E0) are given by assuming a potential of
0.40 V for the cathode reaction. All potentials are reported vs. the
oxygen cathode. Thus, alkaline solutions are commonly used
standard hydrogen electrode (SHE).
for aqueous electrolyte-based metal–air batteries. Table 1 lists

2174 Chem. Soc. Rev., 2012, 41, 2172–2192 This journal is c The Royal Society of Chemistry 2012

Accordingly, adsorption of spectator ions in alkaline media
should be decreased to a great extent, giving rise to more facile
electrocatalytic processes than that in acidic media.28 A notable
disadvantage of using alkaline electrolytes includes carbonate
precipitation due to the reaction between carbon dioxide and
hydroxide (CO2 + 2OH - CO32 + H2O), similar to that in
the case of alkaline fuel cells.31 The poor solubility of carbonates
in alkaline media may cause clogging of electrode pores and
thereby blocking of electrolyte channels. To circumvent this
Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
drawback of CO2 sensitivity, it is helpful to feed purified air or
employ a selective membrane that is permeable to O2. Moreover,
the use of a circulating electrolyte is beneficial as the saturation
of carbonate is attained much more slowly than that in immo-
bilized electrolyte.
The cathode oxygen reduction is a series of complex electro-
chemical reactions, which are proposed to involve multistep
electron-transfer processes and complicated oxygen-containing
species such as O, OH, O2 and HO2 .28,29,31,32 In alkaline
electrolytes, the related cathode reactions can be briefly given as:
O2 + 2H2O + 4e - 4OH (E0 = 0.40 V) (1)
O2 + H2O + 2e - HO2 + OH 0
(E = 0.07 V) (2)
HO2 + H2O + 2e - 3OH (E0 = 0.87 V) (3)
2HO2 - 2OH + O2 (4)
As has been well documented, oxygen reduction may proceed
via a four-electron (4e) pathway or a two-electron (2e) pathway
on surfaces of metals.28,29,31,32 The ORR pathways and mechan-
isms may vary with the catalytic materials applied. Even for the
same catalyst, the ORR behaves as a structure-sensitive reaction.
Different configurations of oxygen adsorption exist on active
sites of catalyst (Fig. 3a), depending on the crystallographic
structure (surface geometry) and the binding energy. The O2
adsorption configurations and the O2-surface interactions affect
the ORR pathways.29,33 For the end-on manner, only one O
atom is coordinated perpendicularly to the surface and one
electron transfer is favored, contributing mainly to the 2e path-
way (Fig. 3b and eqn (2)) with peroxide generation. In contrast,
the parallel coordination with two O atoms adsorbed on the
surface favors O2 dissociation and more likely leads to the direct
4e ORR pathway (Fig. 3c and eqn (1)) without peroxide
formation. The 2e oxygen reduction may be followed by either
another further 2e reduction of peroxide (eqn (3)) or a chemical
disproportionation of peroxide (eqn (4)). This process can be
described as a serial 2  2e pathway.
In the case of metal oxides, the surface charge distribution is
different from that of a metal. The surface cations of stoichio-
metric oxides are not fully coordinated with oxygen. Anion
coordination is completed by the oxygen of H2O in aqueous
solution. Reduction of a surface cation is charge-compensated
by protonation of a surface oxygen ligand. Accordingly, a
four-step catalytic mechanism has been proposed for the ORR
pathway on the surfaces of transition-metal oxides (Fig. 3d).31
This proposal includes steps of surface hydroxide displace-
ment, surface peroxide formation, surface oxide formation,
and surface hydroxide regeneration. The competition between
the O22 /OH displacement and OH regeneration is found to
be rate-limiting for the ORR kinetics in alkaline electrolyte.34
This journal is c The Royal Society of Chemistry 2012
View Article Online
Fig. 3 (a) Different configurations of O2 adsorption on catalyst
surfaces: on top end-on, bridge end-on, bridge side-on one site,
and bridge side-on two sites, from left to right. Simplified electro-
chemical catalysis process of the ORR on metal surfaces in the case of
(b) end-on O2 adsorption, and (c) bidentate O2 adsorption, corres-
ponding to the 2e reduction (with generated peroxide species) and the
direct 4e reduction, respectively. (d) One of the proposed catalytic
ORR pathways at a metal oxide/alkaline electrolyte interface.
Both the above mentioned 4e and 2e reaction schemes may
occur concomitantly and compete with each other. Recent
experimental study and mathematical modelling have shown
that dual-path ORR mechanisms comprising both direct 4e
and series 2  2e pathways exist on carbon-supported Pt
nanoparticles.35 In high potential intervals, the direct path is
dominating, while at low potential the reduction switches to
the peroxide-mediated path. In addition, transport effects such
as desorption and re-adsorption of intermediates play an
important role in the kinetics and pathway-selectivity of the
ORR.36 Non-covalent interactions between hydrated alkali-
metal cations and adsorbed species on active sites also exert
significant effect on the ORR characteristics.37 The real
surface reactions may be masked due to limitation of analysis
techniques, and hence there are possibly more underlying
pathways. Furthermore, if the serial reduction or chemical
decomposition of intermediate species proceeds extremely
quickly, the generated peroxide would be simultaneously
reduced to hydroxide and thus the overall process could be
also viewed as an apparent 4e reduction reaction. For example,
previous studies have shown that manganese oxides are highly
catalytically active toward the peroxide decomposition and/or
reduction, and results in a detected ORR with apparent quasi-4e
transfer.38–42 Therefore, the determination of an explicit ORR
mechanism may be a challenging task in many cases.
The direct 4e oxygen reduction is desirable due to its high
energy efficiency, while the 2e pathway is unfavorable since the
produced peroxide species are corrosive and can cause pre-
mature degradation of the electrochemical cell.22,31 It is now
generally recognized that the 4e reduction predominates on
noble metals whereas the 2e reduction primarily participates
Chem. Soc. Rev., 2012, 41, 2172–2192 2175

on carbonaceous materials.24,43 For transition-metal oxides
and metal macrocycles, various ORR pathways exist, relying
on the specific crystal structure, molecular composition, or
experimental parameters.43,44 The electrochemical character-
istics of different catalytic materials will be discussed in detail
in section 3.
2.2 Organic electrolyte configuration
The aqueous electrolyte configuration is featured with prominent
Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
virtues of low cost, wide availability and high ionic conduc-
tivity. However, for electrochemical processes occurring in
aqueous media, the working potential window is limited
to the potential range within which H2O is stable against
evolution of hydrogen or oxygen. Consequently, although
metal–air batteries such as the Al and Mg-based cells have
high theoretical voltages (Table 1) of approaching or exceed-
ing 3 V, the practical voltages are far below such values when
aqueous electrolytes are applied. Particularly, the reaction
between lithium and water is dangerous, making metallic
lithium unsafe to operate directly at an aqueous environment.
As a result, the aqueous Li-system requires a specially
designed water-stable layer or membrane (e.g., film composed
of solid-state Li+ conducting glass-ceramic materials) to
protect the Li anode.26,45–49 Even so, there has been little
evidence that the electrochemical cathode and anode reactions
are reversible within an aqueous system. Instead, successful
demonstration of electrically rechargeable metal–air batteries
is on the basis of organic electrolytes. Herein, the aprotic
configuration is discussed, with focus laid on the recharge-
able Li–air system since it has triggered intensive current
interest.
The profile of a non-aqueous Li–air battery is similar to a
conventional lithium battery using electrolyte of lithium salt
dissolved in aprotic solvents. The most notable difference lies
in the cathode. For a classic Li battery, the cathode is a lithium
intercalation-material undergoing cathode reactions of Li+
uptake/removal. The cathode active material of a Li–air
battery is O2, which is not stored in the cathode but is drawn
from outside the cell. The cathode reactions of an aprotic
Li–air cell differ from the Li-intercalation process. The possible
net reactions of a Li–air battery are envisioned as follows, with
four or two electrons transferred per molecular O2.8,9,15,19,20,26
4Li + O2 - 2Li2O (E0 = 2.91 V vs. Li+/Li) (5)
2Li + O2 - Li2O2 (E0 = 2.96 or 3.10 V vs. Li+/Li) (6)
The reported standard cell potential of eqn (6) is not uniform,
which may be derived from different Gibbs free energies.
Because of the close E0 values of the above two reactions,
either lithium oxide or lithium peroxide is highly thermo-
dynamically feasible to be the discharge product. Despite the
apparent simplicity of eqn (5) and (6), the detailed mechanism
of the cathode reaction is far from having been definitively
and quantitatively clarified. Like the oxygen reduction in
aqueous media, the cathode reaction in aprotic electrolytes is
a complex process involving stepwise reactions and several
oxygen-containing species. Different mechanisms have been
suggested to interpret the cathode reactions of the aprotic
Li–air cells.
2176 Chem. Soc. Rev., 2012, 41, 2172–2192
View Article Online
According to electrochemical analysis, Laoire et al.
proposed the following scheme for the possible cathode
reactions.50,51
O2 + Li+ + e - LiO2 (7)
2LiO2 - Li2O2 + O2 (8)
LiO2 + Li+ + e - Li2O2 (9)
+
+ 2e - 2Li2O
Li2O2 + 2Li (10)
This mechanism states a first one-electron reduction of oxygen
to superoxide followed by a further reduction of superoxide to
peroxide via another one-electron reaction. Interestingly, the
reduction mechanism is strongly influenced by the solvent and
the supporting electrolyte. In solutions containing large
cations, the cathode reaction proceeds through a one-electron
reversible process with the O2/O2 redox couple, whereas in
the Li+-containing electrolyte, the oxygen reduction reactions
are irreversible or quasi-reversible processes, to form different
products including O2 , O22 and O2 .51 The cation effect on
mechanism and product can be interpreted using Pearson’s
hard–soft acid–base theory coupled with the different relative
stabilities of the Li+–(solvent)n complexes. Lithium ion, super-
oxide and peroxide behave as a hard Lewis acid, a moderately
soft base and a strong Lewis base, respectively. The formation
of Li+–(solvent)n complexes would lower the acidity of Li+, in
rough proportion to the donor number of the solvent. Solvents
with high donor number provide increased stability of the
Li+(solvent)n–O2 and thus result in reversible O2/O2 . In
solvents with low donor number, O2 quickly decomposes to
O22 or may be fully electrochemically reduced to O2 .
Using density functional theory (DFT), Hummelshøj et al.
described an alternative cathode reaction mechanism involving
the following two steps:52
Li+ + e + O2 + * - LiO2* (11)
Li+ + e + LiO2* - Li2O2 (12)
where * denotes a surface site on Li2O2 where the growth
takes place. Given this mechanism, the free energy diagram of
surface-bound species and intermediates estimated from DFT
qualitatively explains the large asymmetry observed experi-
mentally between the discharge and the charge overpotentials
(see for example, in Fig. 6). The DFT calculation also indicates
that during charge, the formation of Li vacancies is thermo-
dynamically favoured and the vacancies are mobile from
surface to bulk, which will pin the Fermi level at the top of
the antibonding peroxide p*(2px) and p*(2py) levels in the
Li2O2 valance band.52,53 Thus, the existence of neutral Li
vacancies in the Li2O2 surface is essential to generate electrical
conductivity for the operation of a Li–air battery since Li2O2
is an insulator. Questions remain how the initial nucleation
of Li2O2 proceeds at the cathode and whether the surface
conductivity can maintain fast electrochemical growth of
Li2O2 on Li2O2 deposits.
Experimental evidences such as ex situ Raman spectra and
powder X-ray diffraction (XRD) data have demonstrated that
Li2O2 predominates the discharge product of the cathode of an
aprotic Li–air cell.8,20 Recently, in situ spectroscopic studies
This journal is c The Royal Society of Chemistry 2012

have further proved that LiO2 is an intermediate on O2
reduction in non-aqueous solvent.54 In situ surface enhanced
Raman spectroscopy (SERS) and in situ differential electro-
chemical mass spectroscopy (DEMS) provide direct evidence
that oxygen is first reduced to intermediate superoxide, which
then disproportionates to peroxide (see eqn (7) and (8)). How-
ever, on reverse charging the cathode, Li2O2 decomposes
directly in a one-step reaction to evolve O2, without a LiO2
intermediate pathway.54 Although being presented as the inter-
Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
mediates, the superoxide species are highly oxidizing and
reactive and can induce several additional side reactions.55,56
Nonaqueous electrolytes used up to date for Li-based
battery chemistries include alkyl carbonates (e.g., ethylene
carbonate, propylene carbonate, dimethyl carbonate or their
combination), ethers (e.g., dioxolane, tetrahydrofuran), and
esters (butyrolactone), which have high oxidation stability
and solvate lithium salts such as LiPF6, LiN(SO2CF3)2 and
LiSO3CF3.57 In the widely employed aprotic organic carbonate-
based electrolytes, the discharge products of the air electrode
contain a series of carbonate species but with almost no Li2O2,
as a result of electrolyte decomposition.58 Very recently,
detailed investigations of the Li–O2 battery with carbonate elec-
trolyte have shown that discharging the cathode forms
C3H6(OCO2Li)2, Li2CO3, HCO2Li, CH3CO2Li, CO2 and H2O
(Fig. 4), which have been specifically identified by the combi-
nation of XRD, SERS, DEMS, NMR and FTIR analyzing
techniques.59 On recharging, oxidation of these carbonate
species occurs with evolution of H2O and CO2. The charge/
discharge pathway in the absence of reversible Li2O2 formation
is inconsistent with most of previously proposed mechanisms
but on the other hand, could explain the discharge/charge
voltage gap and the gradual capacity fade widely observed in
Li–O2 cells. The formation of carbonate species may consume
electrolyte and accumulate in the air electrode, thus degrading
the electrode performance and causing poor rechargeability of
the batteries. The stability of the electrolyte could be further
Fig. 4 Proposed reaction scheme of the formation of discharge products in a Li–O2 battery with alkyl carbonate electrolytes. The discharged
compounds include Li propyl dicarbonate, Li formate, Li acetate, Li2CO3, CO2 and H2O, as marked in red. Reprinted with permission from
ref. 59. Copyright 2011, American Chemical Society.
This journal is c The Royal Society of Chemistry 2012
View Article Online
reduced in the presence of catalysts, which can accelerate para-
sitic reactions. Recognition of electrolyte decomposition there-
by implies that compatible electrolytes need to be developed for
Li–air batteries with sustainable cycling performance. In this
regard, alternative electrolytes such as boron esters, ethers,
ionic liquids and solid-state electrolytes (e.g., Li+-conducting
polymer or ceramic) may have some advantages and deserve
further research.60–64
Compared with the above mentioned catalyst-indispensable
cathode reactions in aqueous electrolytes, oxygen reduction
can possibly proceed without catalysts in nonaqueous electro-
lytes containing Li+. In addition, the cathode reactions in an
aprotic Li–air battery generate intermediates and products
(either Li2O2 or carbonate species) that are drastically less
dissolvable in the organic electrolyte. The accumulation of
insoluble solids may clog the pores of the air electrode, block
the catalyst surface, and electrically passivate the battery.
The charge transfer and mass transport at the interface of
the cathode are hence limiting factors that affect battery
performance.24 Thus, the specific capacity of a Li–air battery
correlates intimately with the character of the cathode. As
carbonaceous materials often serve and dominate inside the air
electrode, the specific capacity is generally reported relative to
the weight of carbon.
Apart from the mechanisms outlined above, the nature of
catalyst surface may also exert a great effect on the cathode
reaction pathways. By comparing the voltammetry and intrinsic
ORR activity for well defined surfaces of glass carbon as well as
polycrystalline Au and Pt electrodes in aprotic organic electro-
lytes, Lu et al. have shown that the reduction mechanism and the
discharge product likely depend on the catalysts.65 The proposed
first ORR step is the formation of superoxide radicals, which are
weakly adsorbed species and might be solvated by cations or
solvents to diffuse into the bulk of electrolyte. The superoxide
radicals then react with Li+ to form surface-adsorbed LiO2,
which undergo alternative subsequent pathways. For catalysts
Chem. Soc. Rev., 2012, 41, 2172–2192 2177

with relatively weak oxygen chemisorptions (e.g., carbon), LiO2
can be reduced to Li2O2. For catalysts forming a strong bond
with O2 (e.g., Pt), LiO2 is probably reduced with preferential
formation of Li2O. The catalyst-dependent ORR activity66–68
and pathway indicate that mechanistic study on electrode with
composite catalytic materials (e.g., including components of
carbon and metals or metal oxides) may be not straightforward
and the catalyst screening should be performed with more
caution.
Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
In view of the inconsistency among various proposed
mechanisms,8,20,50–54,58,59,65 explicit unraveling the cathode
reactions of metal–air batteries is far from a settled issue
to date. Despite the complexity of cathode reductions, estab-
lishing the detailed pathway and the correlation between
the mechanism/activity and the catalyst is a key first step
to understand the origin of the charge and the discharge
behaviours of metal–air batteries and, is also important and
sometimes prerequisite to guide the development of highly
active air electrodes.
3. Catalytic materials for air electrodes
As the cathode reaction of a metal–air battery is generally a
catalytic electrochemical process, the electrocatalyst in the air
electrode plays a vital role in determining the electrode
performance. ORR catalysts have been the subject of extensive
studies for many years in fuel cells technologies, which involve
invariably cathode oxygen reduction. The cathode catalyst to
a large extent determines the energy conversion efficiency and
is responsible for the high cost of a fuel cell.10–13,31 In
principle, most of the catalytic materials applicable to fuel
cells could also serve in metal–air batteries and so could be
the strategies and techniques to enhance the cathode efficiency.
A variety of materials have been employed as the cathode
catalysts, ranging from noble metals and metal alloys to
carbons, transition-metal oxides/chalcogenides and metal
macrocyclic compounds. Review on the cathode electrocatalysts
can be found in different literatures.22,28,29,31,32,43,44,69,70 In this
section, only selected catalytic materials and examples are
presented, focusing on the most recently reported progress and
those of direct relevance to metal–air batteries.
3.1 Noble metals and alloys
Noble metals such as the Pt-group metals, in particular Pt
itself, have been intensively studied as ORR catalysts for many
decades and continue to spur ongoing interest, because of their
known high stability and superior electrocatalytic activity.
As a result of the relevant well-established knowledge, Pt is
often chosen as a benchmark material in current studies of
alternative catalysts. Platinum nanoparticles well dispersed on
high-surface-area support (e.g., carbon) are the state-of-the-
art ORR electrocatalysts. However, the scarcity and cost of Pt
make it necessity to further increase the catalytic activity and
stability yet reduce the noble metal loading of Pt-based
catalysts. Along this line, tuning the size and morphology of
Pt-based nanostructures to achieve small/dispersive size, high
surface areas and desired highly active facets has proven as
efficient route to improve the ORR properties on a mass
basis.71–74 An interesting method to decrease Pt loading to a
2178 Chem. Soc. Rev., 2012, 41, 2172–2192
View Article Online
fractional amount is supporting Pt monolayers on suitable
metal substrates with specific surfaces, which facilitates kinetics
of O–O bond breaking and hydrogenation of reactive inter-
mediates and results in activity surpassing pure Pt.75 Besides,
the most viable strategy to simultaneously enhance perfor-
mance and lower cost is alloying Pt with other appropriate
noble metals or early transition metals that are less expensive.
Recently, substantial progress has been made in fundamental
understanding the electrocatalytic properties of Pt-based alloys
(or intermetallic compounds).76–82 Study on the Pt3Ni(111)
surface has indicated an unusual electronic structure (the
d-band centre position) and highly structured compositional
oscillation in the near surface region, where the outermost and
third layers are Pt-rich and the second layer is Ni-rich.76 As the
weak interaction between the Pt surface atoms and nonreactive
oxygenated species increases the active sites for O2 adsorption,
the Pt3Ni(111) surface is 10-fold more active than the Pt(111)
surface for the ORR. Electrocatalytic trends in the ORR has
been established in terms of a relationship between the surface
composition, specific activity and the electronic structure of
Pt3M (M = Fe, Co, Ni, Ti, V) surfaces.77 The relationship shows
volcano-type behaviour, where a balance between adsorption
energies of reactive intermediates and surface coverage by
spectator species governs the maximum catalytic activity.
Computational and experimental results have further indi-
cated the volcano relationship for a series of different catalysts
with Pt overlayers (Fig. 5a).78 The oxygen adsorption energy is
thus a good descriptor for the ORR activity. A surface that
binds oxygen 0–0.4 eV more weakly than Pt(111) should
exhibit an activity higher than Pt, with the optimum value at
roughly 0.2 eV. The oxygen adsorption energy on the skins in
turn correlates with the heat of formation of the bulk alloy
(DEalloy, defined as the difference between the total energy of
the alloy and the constituents in metallic form), for a range of
Pt and Pd alloys (Fig. 5b). Based on these findings, Pt3Sc
and Pt3Y binary alloys stand out as the most stable. Notably,
Pt3Y exhibits significant activity improvement over Pt, with
a B60 mV positive shift of half-wave potential and a factor
of 6–10 higher kinetic current density in the range of
0.9–0.87 V.78 Recent experimental investigation has confirmed
the superb stability and activity of Pt–Y alloy.81 The kinetic
current density of Pt–Y electrode depends on the alloy com-
position, showing a volcano curve trend with the maximum at
Pt70Y30. The ORR stability is associated with the number
of d-band vacancies of Pt, which correlates with the degree of
alloying and the lattice stain.81 In regard to the screening of
Pt-based alloy catalysts, the surface stability at high electro-
chemical potentials is demonstrated to be a sensitive measure
according to a recent theoretical study on a group of Pt2M
skin alloys.82 Maintaining a zero O coverage is required to
attain high stability as the dissolution of surface atoms in
alloys is significantly facilitated with increasing O coverage.
Furthermore, the surface corrosion energy and the free energy
barrier to OOH dissociation are identified as quantitative
descriptors for tuning catalyst composition. Accordingly,
Pt2Mo achieves considerable stability and activity because of
low overall kinetic barrier for the ORR.82
In addition to the influence of composition, the structure
of Pt-alloys also exerts a prominent effect on the catalytic
This journal is c The Royal Society of Chemistry 2012

Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
Fig. 5 Pt-alloys for electrocatalysis of the oxygen reduction reaction
(ORR): (a) Volcano plots of the oxygen reduction kinetic current
density (jk) as a function of the calculated oxygen adsorption energy
(DEo); (b) computational results showing the relationship between
the oxygen binding energy on Pt/Pd skin surfaces and alloying energy.
Data are shown relative to Pt while circles and squares in (b) represent
50 and 25% of the alloying element in the second layer. Reprinted
with permission from ref. 78. Copyright 2009, Macmillan Publishers
Limited.
activity and durability. For example, dealloyed Pt–Cu core–
shell structure shows exceptionally high catalytic reactivity for
the ORR.79 Strains are found to form in Pt-enriched shell,
which are supported on a Cu core with a smaller lattice para-
meter. The compressive strain in the shell tunes the electronic
band structure of Pt and weakens the chemisorption of reactive
intermediates, resulting in increased reactivity. Moreover, recent
investigation on FePt nanoparticles has revealed the structure-
dependent catalytic stability by comparing the performance
between face centered cubic (fcc) and face centered tetragonal
(fct) structures.80 In the chemically disordered fcc structure, Fe
and Pt atoms are positioned randomly in the fcc lattice, while in
the chemically ordered fct structure, Fe and Pt atoms are
intermetallically stacked. The fct-FePt exhibits better catalytic
activity and durability towards the ORR, due to the well ordered
intermetallic structure, which preserves compositional and struc-
tural stability and offers catalytically active facets with Pt lying
on the top and Fe locating in the underlayer.80 The FePt
nanoparticles, however, still suffer from problems of particle
aggregation and activity decay during prolonged operation due
This journal is c The Royal Society of Chemistry 2012
View Article Online
to Fe loss in aggressive electrolytes. In this respect, we note that
modifying Pt nanoparticles with Au clusters can greatly stabilize
the Pt-based ORR electrocatalysts by raising the Pt oxidation
potential.83
In depth understanding of the effect of composition, struc-
ture, size and shape on the ORR catalytic characteristics of
Pt-based alloys will doubtlessly enlighten our efforts in exploiting,
designing and fabricating more efficient yet economic catalysts.
Concerning the practical application of noble metal-based cata-
lysts in metal–air batteries, their repeated or recyclable use should
be imperative. One can easily conceive that rechargeable metal–
air batteries, owing to the materials-saving character, seem to be
suitable to accept the noble metal catalysts. However, satisfactory
rechargeability of metal–air cells remains a formidable challenge
requiring rechargeable air electrodes. The cathode oxygen reac-
tions are generally irreversible with slow kinetics, as discussed in
section 2. To realize the cycling of an air electrode, we need to find
a catalyst capable of accelerating the ORR upon discharging and
mediating the OER on charging. Fortunately, noble metals can
serve as electrocatalysts for both the ORR and the OER.22
Furthermore, gaining a synergistic effect is possible by combing
one metal that is highly active for the ORR and another metal
that is highly active for the OER to form a bifunctional catalyst.
Indeed, recent application of PtAu nanoparticles in Li–O2 cells
has showed much promise.84 As shown in Fig. 6, PtAu/C delivers
discharge voltages comparable to that of Au/C and charge
voltage comparable to that of Pt/C. Surface Au and Pt atoms
contribute to the ORR and OER kinetics, respectively. Conse-
quently, the overall voltage gap between discharge and charge is
significantly reduced in PtAu, conferring a round-trip efficiency
(defined as the ratio of discharge to charge voltages) of about
77% for the as-assembled Li–O2 cell. Whether this bifunctional
catalyst can lead to better cycling performance, however, still
remains to be seen.
Cheaper precious metals such as palladium and silver and
their alloys have also been the subject of many investigations
because of their modest activity and relatively higher
abundance.85–97 In particular, Ag exhibits reasonably activity
and stability with the price only about 1% that of Pt, rendering
it as an attractive ORR catalyst.28 Compared to Pt, Ag is relatively
less stable and less electrocatalytically active in acidic media.
Fig. 6 Li–O2 battery operated with different catalyst: (a) initial
galvanostatic discharge/charge profiles of Au/C, Pt/C and PtAu/C at
100 mA g 1carbon; (b) discharge/charge curves at different current
densities. The horizontal dashed line marks the nominal equilibrium
potential of O2/Li2O2. Reprinted with permission from ref. 84.
Copyright 2010, American Chemical Society.
Chem. Soc. Rev., 2012, 41, 2172–2192 2179

The electrocatalytic ORR on Ag(111) single crystal surface
shows pH-dependent behaviour.87 The ORR in 0.1 M HClO4
occurs as a 2e, a mixed 2e and 4e, and a 4e reduction process
sequentially from low to high overpotentials. Additionally, the
onset potential is shifted negatively to B0.4 mV in acidic
environment. In contrast, in 0.1 M KOH the ORR proceeds
through almost entirely a 4e pathway in the whole potential
range.87 Carbon-supported Ag nanoparticles (Ag/C) also
promote a 4e ORR pathway over a wide potential range in
Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
0.1 M NaOH solution.94 Furthermore, recent studies have
shown that porous Ag membranes provide electrocatalytic
function (with high exchange current density), mechanical
support and a means of current collection in alkaline
cathodes.93,95 Thus, silver-based catalysts are more adaptive
to be used in alkaline electrolytes and are promising cathode
materials with good balance between cost and performance.
3.2 Carbonaceous materials
The exclusive use of platinum is not feasible for the future
widespread deployment of electrochemical devices based on
oxygen electrodes.98,99 Development of well-performing noble
metal-free cathode catalysts is the ultimate solution to the
obstacle of Pt cost and scarcity.43,44,69,70,98,99 One of the
most inexpensive alternatives is carbonaceous materials, which
have attracted extensive attention either as catalyst supports
or as metal-free catalysts in electrocatalytic chemistry of
oxygen.100–138 Carbons generally provide notable merits
including low cost, wide availability, wettability, large surface
areas, high electrical conductivity and good stability under
harsh environments.101 The most developed cathode catalysts
are usually supported on finely divided carbon with nanoscale
particle size and good dispersion.
Carbon materials exist in a variety of forms with different
electronic, optical, spectroscopic and electrochemical properties.102
Carbon atoms can be sp3 hybridised or sp2 hybridised and
arranged in a diamond or graphite structure. The completely
sp3 hybridised carbon with tetrahedral bonding is featured
with hardness and low electrical conductivity and thus is
uninteresting as an electrode material without intentional intro-
duction of functional dopants. The sp2 hybridised carbon
materials have abundant allotropes including different poly-
morphisms of graphites (e.g., glass carbon, carbon fibers, highly
oriented pyrolytic and natural crystalline graphite, etc.),
fullerene, graphene, carbon nanotubes, and so on. The graphitic
materials are suited to electrode applications because of favour-
able electrical conducting properties.102
It is worth noting that the electrochemical performance
of graphitic electrodes varies with the interior structure,
morphology, and surface effects such as termination and
surface modification. Electrode kinetics may differ signifi-
cantly between the basal plane (parallel to the graphite layer)
and edge plane (perpendicular to the graphite layer) within a
graphitic structure. A graphitic structure with a large number
of edge-plane sites (e.g., edge-plane pyrolytic graphite and
multiwalled carbon nanotubes) exhibits higher activity toward
the ORR.103 In addition, the pore size, wall thickness and
wall crystallinity of carbon materials affect their catalytic
performance. As substrate to support metal nanoparticles,
mesoporous carbon with large pore size and thicker crystalline
2180 Chem. Soc. Rev., 2012, 41, 2172–2192
View Article Online
walls is more conductive and oxidant resistant and facilitates
mass transport.104 Furthermore, functionalization of the
carbon support such as by surface modification or doping,
exerts a prominent effect on enhancing the durability of ORR
catalysts. Heteroatom (such as S, P and N) doped carbons
have been extensively investigated.105,106 In particular, nitrogen
has proven to be a very efficient functional component or
dopant to mitigate activity degradation.107–111 Nitrogen can
be incorporated into the graphitic network in the graphitic,
pyridinic and pyrrolic form.109 Doping of nitrogen increases the
degree of defectiveness and edge plane sites in graphitic carbon
materials. The type and content of the nitrogen functional
group affects the following aspects of the catalyst system: the
size and dispersion of the supported metal particles, support/
catalyst chemical bonding, and the electronic structure of
supported catalyst nanoparticles.108,109 These are influential
factors in the catalytic activity and durability toward the
ORR. Taking into consideration the effect of both carbon
forms and nitrogen doping, highly stable and active ORR
catalysts have been obtained by loading Pt nanoparticles on
nitrogen-doped ordered mesoporous carbons.111 Carbons can
be also modified with other materials to improve electrode
performance. For example, carbon nanotubes combined with
tungsten carbide can be used as highly efficient hybrid supports
for Pt electrocatalysts that impart a more positive onset
potential and increased current density.112 In addition, carbon
black shows a two-fold increase of corrosion resistance through
surface modification of tungsten carbide nanoparticles.113
While carbon black materials (e.g., Vulcan XC-72) have
been the most conventional catalyst support in literatures,
increasing interest has been emphasized on carbon materials
with novel texture and morphologies, especially porous carbons
and nanostructured carbons.101,114,115 Carbon nanostructures
can serve not only as catalyst supports but also as catalytically
active components themselves because of different electro-
chemical properties from that of traditional bulk carbon forms.
The peculiar carbon nanostructures include one-dimensional
(1D) nanotubes and nanofibers, 2D graphite and graphene
nanosheets, and nanoporous architectures. Carbon nanotubes
are an efficient substrate for dispersing a catalyst component
(especially Pt nanoparticles) due to facile electronic conductivity
and structural integrity and open structure that facilitates
diffusion of reactants, products and intermediates in and out
of the catalytic layer.116–119 Carbon nanotube-based hybrid
materials generally show remarkably enhanced electrocatalytic
performance due to synergistic effects.120,121 Nitrogen-doped
carbon nanotubes can act as noble-metal free catalysts.122,123
Carbon nanofibers are also potential oxygen electrode
materials.124 Graphene and functionalized graphene materials
have recently attracted increasing interest as metal-free electro-
catalysts for oxygen reduction.125,126 These abundant carbon
nanostructures and their doping or surface modification with
functionalities may enable researchers to well tailor the catalytic
properties.
As one of the typical examples illustrating the viable appli-
cation of carbon nanostructures, vertically aligned nitrogen-
doped carbon nanotubes (VA-NCNTs) can act as a metal-free
electrode to catalyze the 4e ORR in alkaline electrolyte.127 The
VA-NCNTs even outperform their Pt/C counterparts in ORR
This journal is c The Royal Society of Chemistry 2012

activity and durability. Such superb performance and the
unexpected 4e pathway are believed to arise from the incor-
poration of electron-accepting nitrogen atoms in the conjugated
nanotube carbon plane, which impart a high positive charge
density on adjacent carbon atoms, favouring parallel diatomic
adsorption.127 Improved electrocatalytic activity could be
achieved after heat treatment of the nitrogen-doped carbon
nanotubes.128 Moreover, nitrogen-doped porous carbons and
graphenes have also exhibited remarkable ORR activity and
Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
durability comparable to or better than the commercial
Pt/C catalysts.129–132 For instance, 1D nitrogen-doped carbon
nanocapsules, which are synthesized from a single-component
precursor template route, outperform the benchmark Pt/C
catalyst in electrocatalytic activities in alkaline electrolytes (as
shown in Fig. 7).132 The prominent catalytic performances
suggest that carbonaceous materials with nitrogen doping are
promising metal-free ORR electrocatalysts.
However, it should be noted that the nature of the active
sites and the ORR mechanism in the intensively investigated
nitrogen-containing carbon materials have not been clearly
elucidated.133 The generally accepted opinion is that the doped
nitrogen atoms play a crucial role in the ORR. The exposure
of edge planes and the creation of impurity band/surface states
near the Fermi level are also viewed as causes behind the
catalytic activity.134 Functional groups on carbon surfaces are
suggested to modify the electronic band structure and thus
tune the ORR properties.134 Recent DFT calculations imply
that the edge structure of carbon is involved in ORR activity
by lowering the oxygen adsorption barrier and electron transfer
barrier, and meanwhile, the type of doped-N determines the
ORR pathway selectivity.126 Computational study, together
with more direct experimental techniques, will provide much
insight in understanding the carbon-based catalysts.
Application of carbon materials is ubiquitous in air electrodes
for practical metal–air batteries. While carbon itself is catalyti-
cally active toward the ORR (mainly through a 2e pathway), it
serves mainly as a catalyst support and electrical conducting
Fig. 7 Nitrogen-doped carbon nanocapsules (NCNC) as non-noble
electrocatalysts for the ORR in alkaline media: (a) schematic presen-
tation of their fabrication, (b) SEM and (c) TEM images of the
capsules, and (d) linear sweep voltammograms of the NCNC (the
subscript denotes the synthesized temperature) and the benchmark
Pt/C (E-TEK). Reproduced with permission from ref. 132. Copyright
2011, Royal Society of Chemistry.
This journal is c The Royal Society of Chemistry 2012
View Article Online
additive in the air electrode of aqueous Zn–air, Mg–air, and
Al–air batteries.6 In Li–air cells that are relatively less dependent
on catalyst, active carbons in the cathode is capable to sustain
considerable cell performance.8 Recent examples have demon-
strated that carbon nanostructures such as carbon nanofibers
and graphene nanosheets (GNSs) can be used as the cathode
for Li–O2 batteries with both nonaqueous electrolyte and
aqueous–organic hybrid electrolyte.124,135–137 Carbon nanofibers
grown on a porous alumina substrate can be used as binder-
free electrodes that provide gravimetric energies of about
2500 W h kgelectrode 1 at power of about 100 W kg 1.124 In
the nonaqueous Li–O2 cell, GNSs (Fig. 8a) result in high
discharge capacity exceeding 8000 mA h g 1 (Fig. 8c).135 For
the hybrid-electrolyte cell, heat-treated GNSs give rise to
excellent cyclability of up to 50 charge–discharge cycles.136
The performance of GNSs is significantly better than the
comparative BP-2000 and Vulcan XC-72 carbons. The superi-
ority of GNSs derives from the large surface areas, high
electronic conductivity, and the unique structure that provides
3D diffusion channels and numerous active sites/defects at the
edges (as shown in Fig. 8b). Interestingly, pencil-trace (multi-
layered graphene nanosheets) on the surface of a ceramic Li–ion
conducting film can serve as a novel catalytic electrode for
rechargeable Li–air batteries.137 Furthermore, comparing dis-
charge characteristics of Li–air cells with different carbon
cathodes has revealed that the mesopore volume of carbon
materials has a large contribution to the capacity.138 Therefore,
the employment of carbon nanostructures with optimized
Fig. 8 Application of carbonaceous materials in Li–O2 batteries:
TEM image of the graphene nanosheets electrode (a) before and
(b) after discharge (the square marks thicker product deposit, indicating
high activity at the edges); (c) Discharge/charge profiles of Li–O2 batteries
with different carbon cathodes at a current density of 75 mA g 1.
Reproduced with permission from ref. 135. Copyright 2011 Royal
Society of Chemistry.
Chem. Soc. Rev., 2012, 41, 2172–2192 2181

morphologies and textures may offer great opportunity to attain
high-performance metal–air batteries.
3.3 Transition-metal oxides
Transition-metal oxides and in some cases transition-metal
chalcogenides, carbides, nitrides, oxynitrides and carbo-
nitrides represent another family of cathode electrocatalysts
as an alternative to traditional noble metals.99 Their prominent
advantages generally include high abundance, low cost, and
Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
environmental friendliness. Although some of them lack suffi-
cient stability in acidic media, generally they are reasonably
stable in alkaline electrolytes, making these compounds
applicable to electrochemical catalysis. For example, titanium
oxides are demonstrated to be good functionalized cocatalytic
supports for both non-precious metals and noble metals.139–141
Nanostructured titanium oxide supports can modify the
surface electronic structure of Pt and provide high structural
and chemical stability due to strong metal/support inter-
action.141 Titanium nitrides can be used as efficient cathode
electrocatalysts.142 Transition-metal carbides, especially in nano-
size, can also act as promising supports to promote the activity
and stability of Pt or Pd-based ORR electrocatalysts.143,144
Early transition metals of group VII and VIII elements
(e.g., Mn, Fe, Co and Ni) possess multiple valences, resulting
in a variety of oxides and chalcogenides/carbides. For example,
manganese may exist in different valence states of Mn(II),
Mn(III) and Mn(IV), corresponding to abundant and ubiqui-
tous manganese oxides ranging from MnO, Mn3O4 to Mn2O3
and MnO2.145 The combination of two or three transition
metals with oxygen will lead to a series of ternary or quaternary
composite metal oxides. Even for manganese oxides with the
same nominal elemental composition and valence, they are
possibly featured with different crystallographic structures
(Fig. 9). The variable valences and abundant structures of
transition-metal oxides give rise to rich redox electrochemistry
and materials chemistry, providing a vast opportunity for the
search and development of valuable noble metal-free catalysts.
Important progress in transition-metal chalcogenides (especially
the Chevrel-phase compounds and cobalt sulfides/selenides)
can be found in the review presented by Alonso-Vante and
co-workers and the references cited therein.44 We focus herein
on metal oxides (especially Mn-based oxides), which have
been extensively studied as electrocatalysts for air electrodes.
Manganese oxides are of special interest in oxygen electro-
chemistry. One possible reason of the motivation is that
Mn–Ca–O complex cluster is the catalytic active centre of
oxygen evolution in photosystem II in nature.146–148 However,
the complex redox chemistry and different crystallographic
structures of manganese oxides make it rather difficult to
explicitly understand the oxygen reduction and evolution
mechanisms and to clarify the materials properties that govern
the catalytic activity.
Electrochemically active manganese oxides such as Mn5O8,
Mn3O4, Mn2O3, MnO2 and MnOOH all exhibit catalytic
activities towards the ORR in alkaline media.38–43,149,150 The
catalytic ORR mechanism, however, is still in debate. Both a
direct 4e pathway and series 2  2e pathway have been
suggested to interpret the observed apparent overall 4e ORR
process. For MnO2, the direct 4e oxygen reduction proceeds
2182 Chem. Soc. Rev., 2012, 41, 2172–2192
View Article Online
Fig. 9 Presentations of the structures of some binary and ternary
manganese oxides. c- and t-AMn2O4 denote cubic and tetragonal
Mn-based spinels, respectively, with the A-site cations being tetra-
gonally coordinated with oxygen. BMnO3 represents the Mn-based
perovskite with the B-site ions being marked in green. Metal cations in
A, B and Mn sites can be substituted by other metal ions.
through the first proton insertion process to form MnOOH,
the second O2 adsorption onto two neighboring MnOOH
surface sties (via the bridge adsorption-manner), the third
rate-determining electron-transfer step involving electro-
splitting of the adsorbed O2 species to Oads, and the final
electrochemical reduction of Oads to OH .40 In this scenario,
the Mn(III)/Mn(IV) redox couple acts as the oxygen acceptor/
donor mediator and assists the electron transfer. The series
pathway undergoes a first 2e reduction process to intermediate
HO2 and the sequent disproportionation of HO2 .149 The
major difference between the two reaction schemes can be
attributed to the manner of oxygen adsorption on active
surface sites (Fig. 3a). The end-on O2 adsorption does not
favour the breaking of O–O bonds and hence tends to yield
HO2 rather than OH . More study is thus required to clarify
the oxygen adsorption behaviours on the surface of manganese
oxides. Regardless of this uncertainty, the redox reaction between
Mn species with different valence synergistically contributes to
mediate the reduction process in both pathways. The involve-
ment of Mn(IV)/Mn(III) in the ORR electrocatalysis has been
confirmed by in situ X-ray absorption near edge structure
(XANES) study.38
In addition to the ORR mechanism, promoting the develop-
ment of highly active manganese oxide catalysts necessitates a
systematic study on the influential physical and chemical
parameters. It has been demonstrated that factors exerting
an important effect on the catalytic performance may include
composition, structure, phases, valence, morphology, size,
surface area, electrical conductivity, etc.38–42 The influence of
composition on the properties has been scarcely investigated.
One trend is that the ORR catalytic activity correlates with
the Mn valence,149 but a clear relationship remains to be
established. However, it is obvious that the crystallographic
structures and morphologies greatly affect the performance of
manganese oxides.42 For MnO2-based catalysts, the activity
This journal is c The Royal Society of Chemistry 2012

Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
Fig. 10 Polarization curves of different electrodes in KOH aqueous
electrolyte: (a) carbon-supported LaMnO3, (b) LaMnO3/LaNiO3
(10 wt% LaMnO3), (c) LaMnO3/LaNiO3 (30 wt% LaMnO3), (d) neat
LaNiO3. The anodic and cathodic polarization corresponds to the
electrocatalytic OER and ORR process, respectively. Reproduced
from ref. 158 by permission of The Electrochemical Society.
follows an order of a- > b- > g-MnO2, which is attributed to
a combinative effect of their intrinsic tunnel size and electrical
conductivity. For MnO2 catalysts with the same phase, the
nanostructures apparently outperform the micro-sized particles
due to smaller size and higher specific surface areas. Moreover,
the nature of preferentially exposed facets of manganese oxides
would be another influential factor,41 which requires further
investigation. Furthermore, combining manganese oxide with
another electrocatalytic component seems to be an efficient
strategy in enhancing the ORR activity. The obtained composite
catalysts such as manganese oxide nanoparticles electrodeposited
on platinum substrate150 and palladium nanoparticles deposited
on MnO2 nanorods151 are superior to both pristine noble metals
and undecorated manganese oxides.
Like binary manganese oxides, composite manganese oxides
incorporating mixed-valence transition metals have also
attracted extensive interest.24,34,152–158 Extra merits of compo-
site oxides generally include increased structural stability and
the ability to combine one type of active sites favourable for
the ORR and the other type of sites beneficial to the OER,
rendering them possible bifunctional catalysts for air electrodes
that can serve in rechargeable metal–air batteries.159,160
Composite oxides adopting the spinel or perovskite structure
are particularly attractive. The spinel and perovskite structures
allow partial cation substitution (see for example in Fig. 9) to
form a large number of oxides,161,162 enabling researchers to
tune their catalytic properties.
Recent study has shown that the ORR activity of perovskite
family correlates primarily to s*-orbital (eg) occupation and
secondarily to the extent of transition metal–oxygen covalency,
which serve as activity descriptors.34 The design principle for
improving the ORR activity of perovskites is an eg-filling having
a value of B1 for maximum activity, which can be further
enhanced by increasing the covalency between the metal 3d
This journal is c The Royal Society of Chemistry 2012
View Article Online
and oxygen 2p orbitals. Applying such a principle, LaMnO3+d
and LaNiO3 exhibit intrinsic ORR activity comparable to
state-of-the-art Pt/C in alkaline media.34 Nanosized composites
of perovskite-type La1 xSrxMnO3 and carbon nanotubes also
show remarkable electrocatalytic performance.157 Furthermore,
a recent example indicates that a composite electrode con-
sisting of LaMnO3 and LaNiO3 displays excellent bifunctional
ORR/OER activity.158 As shown in Fig. 10, LaNiO3 has high
electrical conductivity and high OER activity while LaMnO3
is highly active for the ORR; their combination offers a benefi-
cial balance between the ORR/OER electrocatalytic activity and
the stability against anodic polarization.158 The prominent bifunc-
tional electrochemical performances of perovskite composites
suggest their promising use in rechargeable metal–air batteries.
Cobalt and manganese spinels are also highly potential
candidates as electrocatalysts for bifunctional air electrodes
because of high catalytic activity and good corrosion stability
in alkaline solutions.153–155 It should be noted that the
preparation method of a spinel oxide greatly influences its
physiochemical properties and electrochemical charac-
teristics.154 Conventional synthesis of crystalline ternary
spinels normally follows the ceramic route and requires a
high heating temperature. Although having a good crystal-
linity, the resulting product often exhibits limited electro-
chemical activity due to large particle size and low surface
areas. Recently, a facile and rapid room-temperature synthetic
methodology has been developed for highly active spinels.156
The preparation is based on a reduction of amorphous MnO2
precursors in aqueous solution containing divalent metal ions
such as Co2+. With preserved morphology resembling the
parent precursor, the prepared Co–Mn–O nanocrystalline
spinels possess high surface areas, numerous defects and
abundant vacancies, and manifest remarkably higher activity
towards the ORR/OER as compared to their counterparts
synthesized at high temperature (shown in Fig. 11). Interest-
ingly, the Co–Mn–O spinels show phase-dependent electro-
lytic characteristics, that is, the cubic phase outperforms the
tetragonal phase in catalyzing the ORR while the trend is in
reverse for the OER. Such phase-dependent character is
attributed to the different oxygen binding ability on the surface
of the two phases, as evidenced from both experimental
and computational analysis.156 Following a similar synthetic
strategy, hollow ZnMn2O4 spinel nanospheres and nanocubes
have also been selectively prepared and show respectable
electrocatalytic performance.163 This demonstrated example
proves the feasibility of rational design and controllable
synthesis of spinel-based bifunctional electrocatalysts for air
electrodes.
The above examples indicate that manganese-based oxides,
especially in the composite form incorporated with another
multivalence transition-metal, should be promising alternative
to Pt-based catalysts in alkaline media. Not surprisingly, they
have already found wide practical applications in alkaline
metal–air batteries (see illustrated examples in ref. 24 and
references cited therein). Very recently, Lee et al. have
reported that Mn3O4 nanoparticles anchored on ionic liquid
modified graphene nanosheets exhibit high ORR catalytic
activity and their use in an Zn–air battery lead to a maximum
peak power density of 120 mW cm 2.164 Applications of
Chem. Soc. Rev., 2012, 41, 2172–2192 2183

Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
Fig. 11 Cobalt–manganese spinel oxides as electrocatalysts for the
ORR and OER. SEM images of (a) tetragonal-phase spinel nano-
structures (RT-t-spinel) and (b) cubic-phase spinel nanostructures
(RT-c-spinel) synthesized at room temperature. Voltammograms of
the (c) ORR and (d) OER recorded on different catalysts. Compar-
isons are also given to the counterpart cubic-phase (HT-c-spinel) and
tetragonal-phase (HT-t-spinel) bulk spinels synthesized using high-
temperature ceramic method. Reproduced from ref. 156. Copyright
2011, Macmillan Publishers Limited.
manganese oxides in aprotic Li–air cells can be also found in
different literatures.20,165–168 When used as catalysts in the
oxygen cathode, manganese oxide nanoparticles supported on
carbon and MnO2 nanowires mixed with carbon can deliver
high capacities with capacity retention for a few charge and
discharge cycles.166,167 Likewise, the combination of Pd and
MnO2 results in stable capacity for 20 cycles and is highly
effective in decreasing the charge potential to nearly its
theoretical value and improving the energy efficiency from
60 to 89%.168 It can be predicted that composite manganese
oxides such as Mn-based spinels and perovskites are also
useful cathode catalysts in rechargeable Li–air batteries.
It should be noted that most of the transition-metal oxides,
owing to their semiconducting character, can not provide as
high a electrical conductivity as in the cases of metal and
carbon-based catalyts. Thus, oxide materials are generally
mixed mechanically with a large amount of carbon powders
to fabricate air electrodes with low resistance. However, the
addition of electrical conducting agent may not only hinder
the interface contact but also lower the loading level of the
active component. An alternative strategy is using hybrid
materials that firmly combine an oxide with a highly conducting
substrate such as carbon nanostructures.120,169,170 The synergistic
coupling of nanomaterials also enables bifunctional electro-
chemical catalysis that can be hardly achieved within a single
component. For example, binary Co3O4 spinel, a material with
considerable OER activity but little ORR activity, when grown
on nitrogen-doped graphene to form a hybrid nanomaterial,
exhibits high performance for both ORR and OER in alkaline
electrolyte according to a latest report.170
Finally, it is relevant to mention here that various classes
of oxide-ion conducting compounds (including some classic
perovskite-based oxides) have been widely used in solid oxide
fuel cells (SOFCs).162 If we take into consideration the flexible
2184 Chem. Soc. Rev., 2012, 41, 2172–2192
View Article Online
structural networks, the rich defect properties and the ionic
transport mechanism of these materials, it is possible that
some of them can be adapted as catalysts in metal–air batteries
as well. Meanwhile, the design concept of cathodes for SOFCs
may be also applicable to air electrodes. Accordingly, transition-
metal oxides along this line are worthy of further studies.
3.4 Inorganic–organic composites
Tremendous effort has been directed to the development of
inorganic–organic composite (this oversimplified term is used
here to intentionally denote the integration of inorganic metal
centre and organic matrix) materials as noble metal-free
catalysts for oxygen electrochemistry.43,98,99,171–192 This promising
family of alternative electrocatalysts include transition-metal
macrocyclic complexes, metal–polymer composites, and the rele-
vant heat-treated derivatives.
Transition-metal macrocycles (e.g., TMPP, PC, TPP and
TAA, molecular structure shown in Fig. 12a–d) have been
extensively investigated from the synthesis methodology to
the catalysis mechanism, as reviewed in detail in several
recent publications.43,99,133,172,173,181 The primary motivation
possibly arises from the intention to mimic the photosynthesis
process in nature that involves metalloporphyrins. Although
having undergone several decades of studies, the catalytic
nature of the metal-macrocyclic family remains elusive. It is
generally believed that C, N and transition-metal (Fe or Co)
are involved in the catalytically active sites, which can be
simply labelled as M–Nx/C (x is normally 2 or 4) species.99,185
However, it is difficult to reach a consensus as to what plays
the predominant role. At least, the functionality of metal is
unclear and in debate.
Recently, the mechanisms of the ORR on carbon-supported
Fe-phthalocyanine (FePc/C) and Co-phthalocyanine (CoPc/C)
catalysts in alkaline media have been elucidated by combining
electrochemical techniques and density functional theory (DFT)
computational study.178 The FePc/C catalyst exhibits a more
positive onset potential and higher current density than that of
CoPc/C. Remarkably, the ORR proceeds via a 4e pathway on
FePc/C while it is through a 2e pathway on CoPc/C (Fig. 13a).
The DFT results indicate that the structure of H2O2 adsorption
is essentially different on the surfaces of the two catalysts
(Fig. 13b). During H2O2 adsorption, the breaking of the O–O
bond enables the 4e ORR on FePc while the absence of O–O
bond cleavage accounts for the 2e reduction. These investiga-
tions thus imply that the metal centers exert a vital effect on
determining the activities and mechanisms of electrocatalytic
ORR on metal macrocyclic compounds.
On the other hand, since some metal-free macrocyclic
compounds (pyridine-like, pyridone-like and graphite-like
species with N/C and without metal such as nitrogen-doped
carbon materials discussed in section 3.2) are highly catalyti-
cally active, metals may be not a necessary part in the active
sites but only participate in creating the active centres consisting
of C and N. Recent study on the role of residual metal in ORR
in CoPc-based carbon catalysts has verified that Co hardly
contributes to the catalytic activity.186 Even if the metal is
indispensable, the coordination character of transition metals
to N and its effect on the catalytic properties have not been fully
understood. In addition, recent study on a CuFe–N/C catalyst
This journal is c The Royal Society of Chemistry 2012

Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
Fig. 12 Structures of some representative transition-metal macrocycles
(a–d) and proposed active sites of some transition-metal macrocycle
composite catalysts (e–g): (a) tetramethoxy tetraphenyl porphyrin
(TMPP), (b) phthalocyanine (PC), (c) tetraphenyl porphyrins (TPP),
(d) tetraazaanulene (TAA), (e) metal-aromatic cycles attached to the
edges of graphitic sheets,177 (f) presumed catalytic moiety derived from
heat treatment of a metal-polyaniline complex in N2,179 and (g) supposed
configuration of metal-polypyrrole composite catalyst.171 M represents a
transition-metal such as Fe, Co, Ni, Mn, etc.
has provided new insight into the functionality of bicore metals:
Fe(III)Nx serves as the active site for ORR and the Cu(II)/Cu(I)
redox mediator functions as the electron shuttle.180 Further-
more, for homogenous catalysts such as cobalt tetraphenyl-
porphyrin, multiple functional groups may participate in the
multi-centred catalytic process to create a concerted action.187
Anyway, the nitrogen presence appears to be an utmost require-
ment for attaining activity. There is also possibility that the
catalytically active sites vary with the composition and structure
of this diverse class of materials. For example, homogeneous
oxygen reduction on metal-free porphyrin involves binding of
molecular oxygen to the protonated free porphyrin base.188 The
different modes of binding and activation of oxygen molecules on
non-metal sites would permit alternative catalytic routes for
metal macrocycles for heterogeneous redox processes. More
fundamental studies are clearly required to identify the nature
of real active sites and elucidate the catalysis mechanism.
Because of the normally insufficient long-term stability
of metal-macrocyclic compounds in strong acidic or alkali
environments, inorganic–organic composite electrocatalysts
are generally prepared by the pyrolysis of a variety of pre-
cursors containing metal, nitrogen and carbon. Their catalytic
activities are found to depend on a series of parameters, such
as the type and content of central metal, the precursors,
This journal is c The Royal Society of Chemistry 2012
View Article Online
Fig. 13 Carbon-supported Fe-phthalocyanine (FePc/C) and
Co-phthalocyanine (CoPc/C) as the ORR catalysts in alkaline
solutions. (a) Voltammetry profiles of FePc/C, CoPc/C, and the
comparative Pt/C recorded on a rotating ring-disk electrode. The disk
and ring current densities are represented by Id and Ir, respectively.
The inset curves display the H2O2 yields on the three catalysts.
(b) Density functional theory (DFT) calculation results showing the
optimized structural configurations for HOOH adsorbed on FePc
(left) and H2OO adsorbed on CoFc. The central yellow ball, the two
red balls, blue balls and light white balls correspond to the Fe/Co, O,
N, C and H atoms, respectively. Reprinted with permission from
ref. 178. Copyright 2009, American Chemical Society.
the supporting substrate, the heat treatment condition, and
the synthesis method.173 The metal-ion centre exerts a signifi-
cant effect on the redox and charge-transfer properties of the
metal macrocycles and the most active metals are Fe and Co.
Logically, a combination of the two would perform even
better. In regard to heat treatment, the temperature, duration,
atmosphere, and treatment method are important parameters.
There is often a trade-off between catalytic activity and stability,
and rationalizing the pyrolysis condition is an interesting
research subject. Dahn and co-workers have investigated the
activity of sputtered M–C–N (M is transition-metal such as V,
Cr, Mn, Fe, Co, and Ni) films for the ORR in acid and alkaline
electrolytes.174–176 The choice of M, the N doping, and the
heat-treatment temperature play important roles in the activity
and stability of the heat-treated MxC1 x yNy catalyst libraries.
The optimum heat-treatment temperature is in the range of
700–900 1C. In alkaline solutions, the activities of the catalysts
follow Co > Ni > Mn > V > Cr, while in acid solutions,
Chem. Soc. Rev., 2012, 41, 2172–2192 2185

the order is Fe > Co > Cr > Ni. The N doping increases the
activity. Although Cr is less active, the CrxC1 x yNy libraries
show good passivation against corrosion.175 These results suggest
that the ORR catalytic performance could be rationalized by
carefully adjusting the influential factors.
The structure of the macrocycles influences the ligand–metal
interaction and the character of the pyrolyzed species, which
however, is not easy to be directly correlated as the pyrolysis
destroys the structure of the precursor. Since nitrogen appears
Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
to be a necessary part in the catalytic centre, increasing
surface nitrogen content is of vital importance in enhancing
the activity. Strategies to increase nitrogen incorporation
include tailoring the nitrogen-containing precursors, utilizing
gaseous (NH3 or CH3CN) etching in the pyrolysis process,
and employing new impregnation approaches.99 With respect
to the carbon support, the identified influential factors are
disordered carbon degree/content and microporosity. According
to previous insights into the catalyst design, Dodelet and
co-workers reported in 2009 the best iron-based catalysts with
ORR catalytic activity comparable to Pt.177 They selected highly
microporous Black Pearl 2000 as the carbon support and used
planetary ball-milling to fill the support pores with pore filler
(1,10-phenanthroline) and iron precursor (ferrous acetate). The
best-performing Fe-based catalyst with the greatest increase in
active site density was obtained by pyrolyzing the mixture first
in argon and then in ammonia. The active sites were believed
to contain iron cations coordinated by pyridinic nitrogen func-
tionalities that were anchored in the interstices of graphitic
sheets within the micropores of the support (illustrated in
Fig. 12e).177 While the initial activity of this catalyst was a
factor of >35 relative to previously reported Fe-based catalysts,
its stability should be improved to meet the requirement of
practical application.
In addition to the relatively expensive and complex macro-
cyclic compounds, heterocyclic conjugated polymers such as
polypyrrole, polyaniline and poly(3,4-ethylenedioxythio-
phene) (PEDOT) are also attractive materials in oxygen
electrocatalysis.171,179,189,190 These polymers are characterized
by low cost, high electrical conductivity, abundant function-
alities and distinct redox properties. They can be utilized as
direct electrocatalysts,189 as bridges between substrate and
catalyst to promote physical and electrical contact,190 as
matrices for incorporating metal ion to create active sites,171
and as nitrogen/carbon precursors for pyrolyzed M–Nx/C
materials.179 For example, polypyrrole is used as a matrix
for entrapping cobalt to generate Co–N active sites (Fig. 12g)
for the ORR.171 Such transition metal–polymer composite
materials prepared via a pyrolysis-free process can deliver
considerable ORR activity with respectable stability over a
long operating time. Compared to this non-pyrolyzed compo-
site, the high-temperature system synthesized using mixture of
precursors of metal and heteroatom polymer exhibits better
activity.
Polyaniline has been proven as a suitable template compounds
for C and N due to its structural similarity to graphite. The heat
treatment of polyaniline could not only facilitate the integration
of N-containing active sites into the partially graphitized carbon
matrix but also benefit uniform distribution and increased
density of N sites on the surface. Consequently, polyaniline
2186 Chem. Soc. Rev., 2012, 41, 2172–2192
View Article Online
derived formulations (Fig. 12f) combine high ORR activity with
performance durability and 4e reduction selectivity.179 Polypyr-
role is also good precursor for pyrolyzed metal-containing
composite ORR catalysts.191,192 Pyrolyzed iron-polypyrrole
mesoporous spheres with honeycomb-like structure and large
volumetric surface area, which increase the active site density
and favour mass transport, can be used as a highly efficient
non-noble ORR catalyst.191 As for other inorganic–organic
composite series, improving these promising catalysts requires
further in-depth mechanistic study on the origin of the intrinsic
activity and stability.
Inorganic–organic composite catalyst materials have been
employed in the air electrodes of laboratory metal–air batteries.
For example, carbon-supported FeCo-EDA catalysts prepared
by pyrolysis of a mixture of iron sulfate, cobalt nitrates and
ethylenediamine (EDA) show outstanding ORR activity and
stability in alkaline electrolyte.182 Compared with the commer-
cial Pt/C catalyst, the FeCo-EDA catalyst exhibits a nearly 3
times higher mass activity and 2.5 times better activity retention
after accelerated degradation testing. The superior performance
is attributed to its good structural stability and morphological
preservation (shown in Fig. 14a and b), in contrast to severe
agglomeration of Pt particles. Single cell performance testing on
the assembled aqueous Zn–air batteries demonstrates higher
polarization current density and higher peak power density
(Fig. 14c and d).182 These results indicate great potential of
FeCo-EDA materials as cathode catalyst for aqueous metal–air
batteries. Catalytic application of metal macrocycles in non-
aqueous Li–air cells has also been reported.183 Pyrolyzed FeCu-
phthalocyanine supported on high surface area carbon black
can simultaneously accelerate the 2e oxygen reduction and
catalyze the chemical disproportionation of Li2O2, resulting in
Fig. 14 Application of FeCo-EDA (ethylenediamine) catalyst in
Zn–air batteries: TEM images of FeCo-EDA (a) before and (b) (b)
accelerated degradation test; single cell performance of (c) polarization
curve and (c) power density for the Zn–air cells made with FeCo-EDA
and Pt/C. Reprinted with permission from ref. 182. Copyright 2011,
Elsevier.
This journal is c The Royal Society of Chemistry 2012

decreased polarization of the cells, increased recovery rate of
open-circuit voltage, and reduced apparent activation energy for
the discharge of the cells.183 Therefore, inorganic–organic compo-
sites are highly valuable candidate cathode catalysts for practical
metal–air batteries, despite relatively fewer application to date.
4. Air electrode structures
One of the key features of an efficient air electrode is the
Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
formation of a high-surface area boundary between the active
phases involved in the oxygen reduction: air, the electrolyte,
the catalyst and the conductor.22 In metal–air cells with
aqueous electrolytes, oxygen is reduced to OH , which is
dissolved into the electrolyte. The electrocatalytic oxygen
reaction occurs at a three-phase contact zone between air,
liquid electrolyte and solid catalyst (except to the extent that
the oxygen may dissolve in the electrolyte), as schematically
shown in Fig. 15a. It is necessary to arrange such a three-phase
interface in the air electrode, where air can diffuse throughout
and electrolyte can be adsorbed in the catalyst surface but
must not flood it to the exclusion of gas. This requires careful
construction of the catalyst layer. The catalyst layer is made
hydrophilic on the electrolyte side but hydrophobic on the gas
side.24 Thus, the surface exposed to air is generally treated
with a water-repellent substance (e.g., paraffin wax or Teflon)
while the side facing electrolyte employs hydrophilic additives.6
The balance between hydrophobic and hydrophilic properties is
significantly important for air electrodes used in aqueous metal–
air batteries.
Oxygen electrochemistry in non-aqueous electrolytes differs
from aqueous electrolytes. In a Li–air cell based on organic
electrolyte, the discharge products (Li2O2 and/or Li2O) are
insoluble in the electrolyte and will precipitate on the surface
of the catalyst, preventing continuous air diffusion and access.
As a result, only the oxygen dissolved in the electrolyte
participates in the oxygen reduction. The cathode reaction
takes place at the electrolyte–catalyst two-phase interface.193
Based on this model, the catalyst layer should be completely
wetted with liquid electrolyte to maximize the reaction areas
for high capacity. In addition, the liquid electrolyte layer on
the catalyst surface should remain as thin as possible to
minimize the transport distance of the dissolved oxygen for
fast kinetics. Meanwhile, the implementation of electrolytes
with high oxygen solubility and fast oxygen diffusivity should
also greatly benefit the improvement of the cathode performance.
In this context, both electrode design and electrolyte adjustment
(e.g., tuning parameters such as composition, solubility, polarity,
viscosity and conductivity) are desirable direction for the develop-
ment of advanced Li–air batteries.26,194
In view of the above demonstrated importance of the inter-
face, the design rationale of the cathode structure should focus
on increasing the interface areas and enhancing air diffusion
and transportation. High specific surface area of catalyst
support is of course a prerequisite. The pore structure also
plays a key role in determining the charge and mass transport
properties of the air electrode. Both experimental results and
modelling have shown the influential role of pore size and
distribution in electrode performance.195–199 For an aqueous
Zn–air battery, the use of activated carbon with high surface
This journal is c The Royal Society of Chemistry 2012
View Article Online
Fig. 15 Illustrated interfaces of air electrodes and proposed electrode
structures. (a) Gas–solid–liquid three-phase interface model in
aqueous electrolyte. (b) Liquid–solid two-phase interface model in
non-aqueous electrolyte; (a) and (b) are adapted from ref. 193 with
significant modification, copyright 2010, Elsevier. (c) Model structure
of air electrode with metal mesh/foam-supported oxygen permeable
membrane (OPM, for filtering out H2O or CO2), gas diffusion layer
(GDL) and catalyst layer (CL). (d) Suggested porous structure of the
catalyst layer with hierarchical macro-/meso-/inter-particle pores for
both efficient electrolyte wetting and gas transportation.
area occupied by macropores and mesopores could lead to
remarkable performance.195 In addition, carbons with ordered
and interconnected mesopores can be used as an efficient
catalyst support that provides inner pores for gas diffusion
and outer surfaces for electrolyte access.200 For a Li–air cell,
an interconnected dual pore system (one catalyzed and one
non-catalyzed) with multiple time-release catalyst is proposed
to increase materials utilization, decrease diffusion limitation,
and supply high power for long term.197 The area-specific cell
capacity can be optimized by use of carbon microstructure and
loading as well as electrode porosity/thickness and electrolyte
amount.198
In practical air electrodes, the detrimental effect of carbon
dioxide and moisture should also be taken into consideration
for aqueous alkaline electrolytes and non-aqueous aprotic
electrolytes, respectively. The presence of CO2 will incur
neutralization of the alkaline electrolyte and precipitation of
carbonate that blocks the diffusion/transport channels. The
inclusion of H2O will cause severe Li anode corrosion and
electrolyte degradation. To address these problems, it is very
helpful to use a membrane that is O2 permeable but can block
the incorporation of CO2 or H2O from air.201,202 The current
collector and electrode support are also influential factors on
the performance. Metal mesh is usually used as the current
collector and the substrate to support the gas diffusion layer
and the catalyst layer. Metal foam is an interesting alternative
because of its highly interconnected open porous network,
which provides electrical conductivity, mass transport path-
way and mechanical flexibility.203 Fig. 15c shows a proposed
model structure of an air electrode, which consists of an oxygen
selective membrane, a gas diffusion layer, and a catalyst layer
supported on metal mesh/foam. The catalyst layer should take
advantage of macro-/mesopores and inter-particle pores for
Chem. Soc. Rev., 2012, 41, 2172–2192 2187

electrolyte wetting (but not flooding) and oxygen diffusion, as
schematically shown in Fig. 15d. It should be noted that
multilayer structures with different catalyst compositions may
be beneficial to bifunctional air electrodes for rechargeable
metal–air batteries.32 Furthermore, since the air electrodes
function mainly as electrocatalyst, ideally they should be con-
structed to be as thin and light as possible in order to allow space
to accommodate more anode materials in the cells. Examples of
thin air cathodes based on composite microstructures have
Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
shown superior battery performance compared to conventional
cathode structures.204
5. Conclusions and outlook
This review has highlighted recent progress in electrochemistry
and materials chemistry of air electrodes for metal–air batteries.
The electrochemical reaction pathways of oxygen reduction have
been discussed in both aqueous media and aprotic electrolytes.
Four categories of catalytic materials ranging from traditional
noble metals/alloys to alternative carbons, metal oxides, and
inorganic–organic composites have been selectively surveyed as
catalysts for air electrodes, with demonstration of electrocatalytic
mechanism, influential factors to catalytic properties, and elec-
trode performance. Some basic design rationales of air electrode
structure have also been presented with proposed models. To
sum up the research advances and efforts, great potential and
huge challenges coexist in this field.
While the metal–air systems (particularly rechargeable
Li–air cells) appear to be very promising contenders as future
power sources for electrified transportation and energy storage,
a series of scientific and technological issues remain to be
settled before they can be found practical applications with
widespread deployment. First, many relevant fundamental
aspects are not fully understood. For example, it is necessary
to clearly unravel the elusive oxygen reaction mechanisms
(e.g., 2e vs. 4e pathways and presence or absence of Li2O2)
and nature of electrocatalyts (e.g., the real active sites), which
is prerequisite to guide the design of high-efficiency air elec-
trodes. Good predictive power arises from in-depth insights
into the catalytic mechanism and the correlation between
materials properties and performance. To gain such insights,
a combination of in situ experimental analysis,54,59 theoretical
investigation,34,52,77,78,156,178 nanoscale probing,205 and atomic-
scale modelling206 would be valuable.
In addition to the requirement of fundamental mechanistic
study, it is of paramount importance to develop highly effi-
cient, inexpensive, environmental benign catalytic materials
for enhancing the kinetics of the sluggish oxygen reduction
reactions. Similar to the case of fuel cells,10,43,70,74,99,181 the
large polarization (overpotential) and slow kinetics at
the cathode appear to be the major challenge that limits the
practical electrochemical performances. Solution to this issue
should resort to highly active catalysts for oxygen reduction
and/or evolution reactions. Functional materials determine
essentially the characteristics of any type of electrochemical
devices including batteries.207 Concerning the air electrodes,
there are a rich variety of candidate materials for the oxygen
electrochemistry, providing great opportunity for us to screen
suitable catalysts for a specific application.
2188 Chem. Soc. Rev., 2012, 41, 2172–2192
View Article Online
Of the four categories of catalytic materials mentioned in
this review, the Pt-based noble metal family generally
possesses virtues of both high activity and favourable stability
but disadvantages of cost and scarcity. Alloying with cheap
transition-metals and using Pt-skin overlayered structure
are effective routes to simultaneously lower the noble metal
loading and further enhance the activity.75–80 The compromise
between cost and performance makes the Pt-based catalysts
more adaptive to material-saving rechargeable metal–air
batteries. Carbonaceous materials, transition-metal oxides,
and composite materials derived from macrocycles or polymers
(M–N/C) are promising abundant and cheap catalysts applic-
able to air electrodes. Carbons in nanostructured form such
as graphene nanosheets and N-doped carbon nanotubes are
attractive due to respectable activity, high electrical conduc-
tivity and chemical stability.132–138 Transition-metal oxides
such as Mn-based spinels and perovskites exhibit considerably
high activity and durability in alkaline electrolytes, and can
serve as bifunctional catalysts for both the ORR and
OER.152–158 The composite M–N/C catalysts enable properties
tuning through adjusting the metal centres and tailoring the
organic functionality.171–190
Proposed future research directions in these non-precious
metal catalytic materials would include: (1) exploiting the effect
of physiochemical parameters (e.g., composition, valence state,
phase, structure, defects, morphology, size, surface area, con-
ductivity, etc.) on the intrinsic catalytic activity, (2) increasing
the density of active sites and their utilization through inno-
vative design of materials and structures, and (3) optimizing
catalyst synthesis strategies and conditions (e.g., precursor,
temperature, duration, atmosphere, procedures) to achieve
better activity and stability. In addition, nanotechnologies
may open new avenues in catalyst development; nanostructured
electrode materials are proven as a valuable option. Further-
more, Nature could help in exploiting new electrocatalysts for
the ORR and OER processes. For example, some enzymes can
efficiently catalyze electrochemical reactions by providing both
redox active sites and intramolecular/interfacial electron trans-
fer pathways.208 Active sites in biological enzymes generally
have a larger flexibility of redox sites and geometry as compared
to the rigid surface of inorganic solid catalysts.209 Mimicking
natural oxygen catalytic processes would aid in searching for
better catalysts.
Rational design of the structure also contributes signifi-
cantly to the performance of an air electrode. The basic
principle is to ensure the formation of high interfacial
contact to facilitate oxygen electrocatalysis. Manipulation the
hydrophobic/hydrophilic properties, the porosity and the
catalyst distribution within the air electrode is required to
permit rapid diffusion and transport of oxygen and allow for
efficient contact between electrolytes and catalysts. Bearing in
mind the similarity between fuel cells and metal–air batteries,
concepts/techniques of cathode design/fabrication adapted in
the former (e.g., bipolar structure) could possibly be applied to
the latter. Likewise, multifunctional architectures (e.g., 3D struc-
ture), which have been employed to elaborately arrange the
components (electrode, current collector, separator, and electro-
lyte) in lithium-ion batteries,210,211 would possibly aid in the
design of metal–air batteries.
This journal is c The Royal Society of Chemistry 2012

Metal anode, separator and electrolyte, although not
emphasized in this article, are also critical factors affecting
the performance of metal–air batteries.15 Lightweight metals
such as Al and Mg are prone to be eroded in aqueous
electrolyte, leading to a serious self-discharge problem. The
anodic product (e.g., Al(OH)3 or Mg(OH)2) may block the
electrode and cause premature degradation of battery perfor-
mance. Optimization of electrolyte composition together
with the addition of corrosion inhibitors and buffering agents
Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
help to reduce the anodic polarization and increase the
Faradaic efficiency of the anode reaction; anode fabrication
with porous and micro/nano structures favours fast sedi-
mentation of metal hydroxides in the electrolyte and contri-
butes to improved anode utilization efficiency.212–215 In Li–air
cells with organic electrolytes, dendrite formation of metallic
lithium and environmental contamination would induce
poor cycle performance and short-circuit risk, as in the case
of other types of lithium-based batteries.216 This problematic
issue could be addressed by using a robust lithium compo-
site electrode, a stable protective layer on the electrode
surface, and alternative electrolytes.9,48,64,217–219 Regarding the
separator, its clogging by undissolvable species (e.g., hydroxides
or carbonates) has a detrimental effect on the capacity and
lifetime of metal–air cells. Optimizing the pore size and ionic
selectivity of separator and introducing a CO2 scrubber can be
beneficial. With respect to the electrolytes, especially organic-
based systems for lithium–air batteries, the stability against
the highly oxidizing cathode environment and the low oxygen
solubility/diffusivity limit the battery performance.26 This limi-
tation requires the development of alternative stable electrolytes
(e.g., ionic liquids) and new strategies (e.g., solvent combi-
nation and flow electrolyte design) to enhance oxygen transport
properties.
Besides, it should be noted that metal–air batteries are
plagued by intrinsic limited power capability and recharge-
ability (although the Li–air cells can sustain several cycles
of repeated charge and discharge) mainly due to the slow
kinetics and irreversibility of oxygen electrochemistry. A
current possible technological solution to the power limitation
is using a hybrid battery system with supercapacitors or other
devices that can deliver high power on demand. The inability
to be electrically recharged can be circumvented by the
application of mechanically rechargeable systems. On the
other hand, attempts to increase the cyclability of metal–air
batteries may rely on the development of innovative catalysts
(feasibly in composite form) that facilitate both oxygen
reduction and evolution. Doubtlessly, realizing the intriguing
promise held by metal–air batteries will require ongoing
research efforts from different disciplines to address the
formidable remaining challenges.
Acknowledgements
The authors acknowledge financial support from the National
973 (MOST Grant No. 2011CB935902), 863 (MOST Grant
No. 2011AA050704), National Natural Science Foundation of
China (NSFC Grant No. 20873071), Cheung Kong Scholar
Innovation Team (MOE Grant No. IRT0927), and Tianjin
High-Tech (10SYSYJC27600).
This journal is c The Royal Society of Chemistry 2012
View Article Online
Notes and references
1 R. M. Dell and D. A. J. Rand, Clean Energy, Royal Society of
Chemistry, Cambridge, 2004.
2 J. R. Owen, Chem. Soc. Rev., 1997, 26, 259.
3 M. R. Palacı́n, Chem. Soc. Rev., 2009, 38, 2565.
4 Z. G. Yang, J. L. Zhang, M. C. W. Kintner-Meyer, X. C. Lu,
D. Choi, J. P. Lemmon and J. Liu, Chem. Rev., 2011, 111, 3577.
5 M. Armand and J. M. Tarascon, Nature, 2008, 451, 652.
6 D. Linden and T. B. Reddy, Handbook of Batteries,
McGraw-Hill, New York, 3rd edn, 2002.
7 B. Peng and J. Chen, Coord. Chem. Rev., 2009, 253, 2805.
8 K. M. Abraham and Z. Jiang, J. Electrochem. Soc., 1996, 143, 1.
9 G. Girishkumar, B. McCloskey, A. C. Luntz, S. Swanson and
W. Wilcke, J. Phys. Chem. Lett., 2010, 1, 2193.
10 B. C. H. Steele and A. Heinzel, Nature, 2001, 414, 345.
11 J. Yang, A. Sudik, C. Wolverton and D. J. Siegel, Chem. Soc.
Rev., 2010, 39, 656.
12 E. Fabbri, D. Pergolesi and E. Traversa, Chem. Soc. Rev., 2010,
39, 4355.
13 Y. Wang, K. S. Chen, J. Mishler, S. C. Cho and X. C. Adroher,
Appl. Energy, 2011, 88, 981.
14 W. Tahil, The zinc air battery and the zinc economy: a virtuous
circle, Meridian International Research, 2007.
15 J. S. Lee, S. T. Kim, R. Cao, N. S. Choi, M. Liu, K. T. Lee and
J. Cho, Adv. Energy Mater., 2011, 1, 34.
16 S. H. Yang and H. Knickle, J. Power Sources, 2002, 112, 162.
17 Y. H. Wen, J. Cheng, S. Q. Ning and Y. S. Yang, J. Power
Sources, 2009, 188, 301.
18 S. Müller, F. Holzer and O. Haas, J. Appl. Electrochem., 1998,
28, 895.
19 J. Read, J. Electrochem. Soc., 2002, 149, A1190.
20 T. Ogasawara, A. Débart, M. Holzapfel, P. Novák and
P. G. Bruce, J. Am. Chem. Soc., 2006, 128, 1390.
21 B. Scrosati and J. Garche, J. Power Sources, 2010, 195, 2419.
22 K. Kinoshita, Electrochemical Oxygen Technology, Wiley,
New York, 1992.
23 P. Sapkota and H. Kim, J. Ind. Eng. Chem., 2009, 15, 445.
24 V. Neburchilov, H. J. Wang, J. J. Martin and W. Qu, J. Power
Sources, 2010, 195, 1271.
25 R. Padbury and X. W. Zhang, J. Power Sources, 2011, 196, 4436.
26 I. Kowalczk, J. Read and M. Salomon, Pure Appl. Chem., 2007,
79, 851.
27 B. D. McCloskey, D. S. Bethune, R. M. Shelby, G. Girishkumar
and A. C. Luntz, J. Phys. Chem. Lett., 2011, 2, 1161.
28 J. S. Spendelow and A. Wieckowshi, Phys. Chem. Chem. Phys.,
2007, 9, 2654.
29 P. A. Christensen, A. Hamnett and D. Linares-Moya, Phys.
Chem. Chem. Phys., 2011, 13, 5206.
30 S. A. Wasileski, M. T. M. Koper and M. J. Weaver, J. Chem.
Phys., 2001, 115, 8193.
31 W. Vielstich, A. Lamm and H. A. Gasteiger, Handbook of
Fuel Cells – Fundamentals, Technology and Applications, Wiley,
Chichester, 2003.
32 L. Jörisen, J. Power Sources, 2006, 155, 23.
33 C. F. Zinola, A. J. Arvia, G. L. Estiu and E. A. Castro, J. Phys.
Chem., 1994, 98, 7566.
34 J. Suntivich, H. A. Gasteiger, N. Yabuuchi, H. Nakanishi,
J. B. Goodenough and Y. Shao-Horn, Nat. Chem., 2011, 3, 546.
35 P. S. Ruvinskiy, A. Bonnefont, C. Pham-Huu and
E. R. Savinova, Langmuir, 2011, 27, 9018.
36 A. Schneider, L. Colmenares, Y. E. Seidel, Z. Jusys, B. Wickman,
B. Kasemo and R. J. Behm, Phys. Chem. Chem. Phys., 2008,
10, 1931.
37 D. Strmcnik, K. Kodama, D. van der Vliet, J. Greeley,
V. R. Stamenkovic and N. M. Marković, Nat. Chem., 2009,
1, 466.
38 F. H. B. Lima, M. L. Calegaro and E. A. Ticianelli, Electrochim.
Acta, 2007, 52, 3732.
39 L. Q. Mao, K. Arihara, T. Sotomura and T. Ohsaka, Chem.
Commun., 2003, 2818.
40 I. Roche, E. Chaı̂net, M. Chatenet and J. Vondrák, J. Phys.
Chem. C, 2007, 111, 1434.
41 F. Y. Cheng, J. Shen, W. Q. Ji, Z. L. Tao and J. Chen, ACS Appl.
Mater. Interfaces, 2009, 1, 460.
Chem. Soc. Rev., 2012, 41, 2172–2192 2189

42 F. Y. Cheng, Y. Su, J. Liang, Z. L. Tao and J. Chen, Chem.
Mater., 2010, 22, 898.
43 A. Morozan, B. Jousselme and S. Palacin, Energy Environ. Sci.,
2011, 4, 1238.
44 Y. J. Feng and N. Alonso-Vante, Phys. Status Solidi B, 2008,
245, 1792.
45 S. J. Visco, B. D. Katz, Y. S. Nimon and L. C. D. Jonghe,
US Pat., 7282295, 2007.
46 S. J. Visco and Y. S. Nimon, US Pat., 7645543, 2010.
47 S. Hasegawa, N. Imanishi, T. Zhang, J. Xie, A. Hirano,
Y. Takeda and O. Yamamoto, J. Power Sources, 2009, 189, 371.
Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
48 T. Zhang, N. Imanishi, Y. Shimonishi, A. Hirano, Y. Takeda,
O. Yamamoto and N. Sammes, Chem. Commun., 2010, 46, 1661.
49 Y. G. Wang and H. S. Zhou, Chem. Commun., 2010, 46, 6305.
50 C. O. Laoire, S. Mukerjee, K. M. Abraham, E. J. Plichta and
M. A. Hendrickson, J. Phys. Chem. C, 2009, 113, 20127.
51 C. O. Laoire, S. Mukerjee, K. M. Abraham, E. J. Plichta and
M. A. Hendrickson, J. Phys. Chem. C, 2010, 114, 9178.
52 J. S. Hummelshøj, J. Blomqvist, S. Datta, T. Vegge, J. Rossmeisl,
K. S. Thygesen, A. C. Luntz, K. W. Jacobsen and J. K. Nørskov,
J. Chem. Phys., 2010, 132, 071101.
53 J. Chen, J. S. Hummelshøj, K. S. Thygesen, J. S. G. Myrdal,
J. K. Nørskov and T. Vegge, Catal. Today, 2011, 165, 2.
54 Z. Q. Peng, S. A. Freunberger, L. J. Hardwick, Y. H. Chen,
V. Giordani, F. Bardé, P. Novák, D. Graham, J. M. Tarascon
and P. G. Bruce, Angew. Chem., Int. Ed., 2011, 50, 6351.
55 F. Mizuno, S. Nakanishi, Y. Kotani, S. Yokoishi and H. Iba,
Electrochemistry, 2010, 78, 403.
56 N. Yabuuchi, K. Yoshii, S. T. Myung, I. Nakai and S. Komaba,
J. Am. Chem. Soc., 2011, 133, 4404.
57 K. Xu, Chem. Rev., 2004, 104, 4303.
58 W. Xu, V. V. Viswanathan, D. Wang, S. A. Towne, J. Xiao,
Z. Nie, D. Hu and J. G. Zhang, J. Power Sources, 2011,
196, 3894.
59 S. A. Freunberger, Y. H. Chen, Z. Q. Peng, J. M. Griffin,
L. J. Hardwick, F. Bardé, P. Novák and P. G. Bruce, J. Am.
Chem. Soc., 2011, 133, 8040.
60 D. Shanmukaraj, S. Grugeon, G. Gachot, S. laruelle,
D. Mathiron, J. M. Tarascon and M. Armand, J. Am. Chem.
Soc., 2010, 132, 3055.
61 M. C. Buzzeo, O. V. Klymenko, J. D. Wadhawan, C. Hardacre,
K. R. Seddon and R. G. Compton, J. Phys. Chem. A, 2003,
107, 8872.
62 T. Kuboki, T. Okuyama, T. Ohsaki and N. Takami, J. Power
Sources, 2005, 146, 766.
63 J. Read, J. Electrochem. Soc., 2006, 153, A96.
64 B. Kumar, J. Kumar, R. Leese, J. P. Fellner, S. J. Rodrigues and
K. M. Abraham, J. Electrochem. Soc., 2010, 157, A50.
65 Y. C. Lu, H. A. Gasteiger, E. Crumlin, R. McGuire and
Y. Shao-Horn, J. Electrochem. Soc., 2010, 157, A1016.
66 A. Débart, J. L. Bao, G. Armstrong and P. G. Bruce, J. Power
Sources, 2007, 174, 1177.
67 Y. C. Lu, H. A. Gasteiger, M. C. Parent, V. Chiloyan and
Y. Shao-Horn, Electrochem. Solid-State Lett., 2010, 13, A69.
68 V. Giordani, S. A. Freunberger, P. G. Bruce, J. M. Tarascon and
D. Larcher, Electrochem. Solid-State Lett., 2010, 13, A180.
69 B. Wang, J. Power Sources, 2005, 152, 1.
70 L. Zhang, J. J. Zhang, D. P. Wilinson and H. J. Wang, J. Power
Sources, 2006, 156, 171.
71 K. Yamamoto, T. Imaoka, W. J. Chun, O. Enoki, H. Katoh,
M. Takenaga and A. Sonoi, Nat. Chem., 2009, 1, 397.
72 B. Lim, M. Jiang, P. H. C. Camargo, E. C. Cho, J. Tao, X. Lu,
Y. Zhu and Y. N. Xia, Science, 2009, 324, 1302.
73 Z. Y. Zhou, N. Tian, J. T. Li, I. Broadwell and S. G. Sun, Chem.
Soc. Rev., 2011, 40, 4167.
74 Y. H. Bing, H. S. Liu, L. Zhang, D. Ghosh and J. J. Zhang,
Chem. Soc. Rev., 2010, 39, 2184.
75 J. Zhang, M. B. Vukmirovic, Y. Xu, M. Mavrikakis and
R. R. Adzic, Angew. Chem., Int. Ed., 2005, 44, 2132.
76 V. R. Stamenkovic, B. Fowler, B. S. Mun, G. Wang,
P. N. Ross, C. A. Lucas and N. M. Markovic, Science, 2007,
315, 493.
77 V. R. Stamenkovic, B. S. Mun, M. Arenz, K. J. J. Mayrhofer,
C. A. Lucas, G. Wang, P. N. Ross and N. M. Markovic,
Nat. Mater., 2007, 6, 241.
2190 Chem. Soc. Rev., 2012, 41, 2172–2192
View Article Online
78 J. Greeley, I. E. L. Stephens, A. S. Bondarenko, T. P. Johansson,
H. A. Hansen, T. F. Jaramillo, J. Rossmeisl, I. Chorkendorff and
J. K. Nørskov, Nat. Chem., 2009, 1, 552.
79 P. Strasser, S. Koh, T. Anniyev, J. Greeley, K. More, C. Yu,
Z. Liu, S. Kaya, D. Nordlund, H. Ogasawara, M. F. Toney and
A. Nilsson, Nat. Chem., 2010, 2, 454.
80 J. Kim, Y. Lee and S. H. Sun, J. Am. Chem. Soc., 2010,
132, 4996.
81 S. J. Yoo, S. K. Kim, T. Y. Jeon, S. J. Hwang, J. G. Lee,
S. C. Lee, K. S. Lee, Y. H. Cho, Y. E. Sung and T. H. Lim,
Chem. Commun., 2011, 47, 11414.
82 G. F. Wei and Z. P. Liu, Energy Environ. Sci., 2011, 4, 1268.
83 J. Zhang, K. Sasaki, E. Sutter and R. R. Adzic, Science, 2007,
315, 220.
84 Y. C. Li, Z. C. Xu, H. A. Gasteiger, S. Chen, K. Hamad-Schifferli
and Y. Shao-Horn, J. Am. Chem. Soc., 2010, 132, 12170.
85 F. B. H. Lima, C. D. Sanches and E. A. Ticianelli, J. Electrochem.
Soc., 2005, 152, A1466.
86 J. R. Varcoe, R. C. T. Slade, G. L. Wright and Y. L. Chen,
J. Phys. Chem. B, 2006, 110, 21041.
87 B. B. Blizanac, P. N. Ross and N. M. Markovic, Electrochim.
Acta, 2007, 52, 2264.
88 F. H. B. Lima, J. Zhang, M. H. Shao, K. Sasaki,
M. B. Vukmirovic, E. A. Ticianelli and R. R. Adzic, J. Phys.
Chem. C, 2007, 111, 404.
89 A. E. S. Sleightholme, J. R. Varcoe and A. R. Kucernak,
Electrochem. Commun., 2008, 10, 151.
90 A. Sarkar, A. V. Murugan and A. Manthiram, J. Mater.
Chem., 2009, 19, 159.
91 J. J. Han, N. Li and T. Y. Zhang, J. Power Sources, 2009,
193, 885.
92 N. N. Kariuki, X. Wang, J. R. Mawdsley, M. S. Ferrandon,
S. G. Niyogi, J. T. Vaughey and D. J. Myers, Chem. Mater., 2010,
22, 4144.
93 F. Bidault and A. Kucernak, J. Power Sources, 2010, 195, 2549.
94 J. S. Guo, A. Hus, D. Chu and R. R. Chen, J. Phys. Chem. C,
2010, 114, 4324.
95 W. Tang, L. Zhang and G. Henkelman, J. Phys. Chem. Lett.,
2011, 2, 1328.
96 M. Shao, T. Yu, J. H. Odell, M. Jin and Y. N. Xia,
Chem. Commun., 2011, 47, 6566.
97 F. Bidault and A. Kucernak, J. Power Sources, 2011, 196, 4950.
98 F. Jaouen, E. Proietti, M. Lefèvre, R. Chenitz, J. P. Dodelet,
G. Wu, H. T. Chung, C. M. Johnston and P. Zelenay, Energy
Environ. Sci., 2011, 4, 114.
99 Z. W. Chen, D. Higgins, A. P. Yu, L. Zhang and J. J. Zhang,
Energy Environ. Sci., 2011, 4, 3167.
100 B. Šljukić, C. E. Banks, S. Mentus and R. G. Compton, Phys.
Chem. Chem. Phys., 2004, 6, 992.
101 Y. Y. Shao, J. Liu, Y. Wang and Y. H. Lin, J. Mater. Chem.,
2009, 19, 46.
102 R. L. McCreery, Chem. Rev., 2008, 108, 2646.
103 M. Gara and R. G. Compton, New J. Chem., 2011, 35, 2647.
104 D. Banham, F. Feng, T. Fürstenhaupt, K. Pei, S. Ye and V. Birss,
J. Power Sources, 2011, 196, 5438.
105 C. H. Choi, S. H. Park and S. I. Woo, Green Chem., 2011, 13, 406.
106 X. G. Bao, D. von Deak, E. J. Biddinger, U. S. Ozkan and
C. M. Hadad, Chem. Commun., 2010, 46, 8621.
107 D. von Deak, E. J. Biddinger and U. S. Ozkan, J. Appl.
Electrochem., 2011, 41, 757.
108 Y. K. Zhou, K. Neyerlin, T. S. Olson, S. Pylypenko, J. Bult,
H. N. Dinh, T. Gennett, Z. P. Shao and P. O’Hayre, Energy
Environ. Sci., 2010, 3, 1437.
109 S. Pylypenko, A. Queen, T. S. Olson, A. Dameron, K. O’Neill,
K. C. Neyerlin, B. Pivovar, H. N. Dinh, D. S. Ginley, T. Gennett
and R. O’Hayre, J. Phys. Chem. C, 2011, 115, 13667.
110 H. S. Oh, J. G. Oh, W. H. Lee, H. J. Kim and H. Kim, Int. J.
Hydrogen Energy, 2011, 36, 8181.
111 S. H. Liu, M. T. Wu, Y. H. Lai, C. C. Chiang, N. Yu and
S. B. Liu, J. Mater. Chem., 2011, 21, 12489.
112 C. H. Liang, L. Ding, C. Li, M. Pang, D. S. Su, W. Z. Li and
Y. M. Wang, Energy Environ. Sci., 2010, 3, 1121.
113 M. H. Shao, B. Merzougui, K. Shoemaker, L. Stolar,
L. Protsailo, Z. J. Mellinger, I. J. Hsu and J. G. Chen, J. Power
Sources, 2011, 196, 7426.
This journal is c The Royal Society of Chemistry 2012

114 I. Dumitrescu, P. R. Unwin and J. M. Macpherson, Chem.
Commun., 2009, 6886.
115 W. M. Zhang, P. Sherrell, A. I. Minett, J. M. Razal and J. Chen,
Energy Environ. Sci., 2010, 3, 1286.
116 S. Zhang, Y. Y. Shao, G. P. Yin and Y. H. Lin, J. Mater. Chem.,
2010, 20, 2826.
117 Y. Yuan, J. A. Smith, G. Goenaga, D. J. Liu, Z. P. Luo and
J. B. Liu, J. Power Sources, 2011, 196, 6160.
118 X. Xie, M. Pasta, L. B. Hu, Y. Yang, J. McDonough, J. Cha,
C. S. Criddle and Y. Cui, Energy Environ. Sci., 2011, 4, 1293.
119 R. J. Liu, S. W. Li, X. L. Xu, G. J. Zhang, Y. Ma and J. N. Yao,
Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
J. Mater. Chem., 2011, 21, 14917.
120 L. Wei, C. Q. Li, H. B. Chu and Y. Li, Dalton Trans., 2011, 40, 2332.
121 Y. P. Zhang, Y. Y. Hu, S. Z. Li, J. Sun and B. Hou, J. Power
Sources, 2011, 196, 9284.
122 T. Fujigaya, T. Uchinoumi, K. Kaneko and N. Nakashima,
Chem. Commun., 2011, 47, 6843.
123 L. Y. Feng, Y. Y. Yan, Y. G. Chen and L. J. Wang, Energy
Environ. Sci., 2011, 4, 1892.
124 R. R. Mitchell, B. M. Gallant, C. V. Thompson and Y. Shao-Horn,
Energy Environ. Sci., 2011, 4, 2952.
125 S. Y. Wang, D. S. Yu, L. M. Dai, D. W. Chang and J. B. Baek,
ACS Nano, 2011, 5, 6202.
126 H. J. Kim, K. Lee, S. I. Woo and Y. S. Jung, Phys. Chem. Chem.
Phys., 2011, 13, 17505.
127 K. P. Gong, F. Du, Z. H. Xia, M. Durstock and L. M. Dai,
Science, 2009, 323, 760.
128 T. C. Nagaiah, S. Kundu, M. Bron, M. Muhler and
W. Schuhmann, Electrochem. Commun., 2010, 12, 338.
129 X. Q. Wang, J. S. Lee, Q. Zhu, J. Liu, Y. Wang and S. Dai,
Chem. Mater., 2010, 22, 2178.
130 W. Yang, T. P. Fellinger and M. Antonietti, J. Am. Chem. Soc.,
2011, 133, 206.
131 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, 760.
132 S. Shanmugam and T. Osaka, Chem. Commun., 2011, 47, 4463.
133 G. Liu, X. Li, J. W. Lee and B. N. Popov, Catal. Sci. Technol.,
2011, 1, 207.
134 R. Kannan, U. Bipinlal, S. Kurungot and V. K. Pillai, Phys.
Chem. Chem. Phys., 2011, 13, 10312.
135 Y. L. Li, J. J. Wang, X. F. Li, D. S. Geng, R. Y. Li and X. L. Sun,
Chem. Commun., 2011, 47, 9438.
136 E. Yoo and H. S. Zhou, ACS Nano, 2011, 5, 3020.
137 Y. G. Wang and H. S. Zhou, Energy Environ. Sci., 2011, 4, 1704.
138 X. M. Ren, S. S. Zhang, D. T. Tran and J. Read, J. Mater.
Chem., 2011, 21, 10118.
139 B. E. Hayden, D. Pletcher, J. P. Suchsland and L. J. Williams,
Phys. Chem. Chem. Phys., 2009, 11, 9141.
140 G. Wu, M. A. Nelson, N. H. Mack, S. Ma, P. Sekhar,
F. H. Garzon and P. Zelenay, Chem. Commun., 2010, 46, 7489.
141 V. T. T. Ho, C. J. Pan, J. Rick, W. N. Su and B. J. Hwang, J. Am.
Chem. Soc., 2011, 133, 11716.
142 J. Chen, K. Takanabe, R. Ohnishi, D. Lu, S. Okada,
H. Hatasawa, H. Morioka, M. Antonietti, J. Kubota and
K. Domen, Chem. Commun., 2010, 46, 7492.
143 Z. F. Hu, C. Chen, H. Meng, R. H. Wang, P. K. Shen and
H. G. Fu, Electrochem. Commun., 2011, 13, 763.
144 S. B. Yin, M. Cai, C. X. Wang and P. K. Shen, Energy Environ.
Sci., 2011, 4, 558.
145 J. E. Post, Proc. Natl. Acad. Sci. U. S. A., 1999, 96, 3447.
146 M. M. Najafpour, T. Ehrenberg, M. Viechen and P. Kurz,
Angew. Chem., Int. Ed., 2010, 49, 2233.
147 Y. Umena, K. Kawakami, J. R. Shen and N. Kamiya, Nature,
2011, 473, 55.
148 I. Zaharieva, M. M. Najafpour, M. Wiechen, M. Humann,
P. Kurz and H. Dau, Energy Environ. Sci., 2011, 4, 2400.
149 L. Q. Mao, D. Zhang, T. Sotomura, K. Nakatsu, N. Koshiba and
T. Ohsaka, Electrochim. Acta, 2003, 48, 1015.
150 M. S. El-Deab and T. Ohsaka, Angew. Chem., Int. Ed., 2006,
45, 5963.
151 W. Sun, A. Hsu and R. R. Chen, J. Power Sources, 2011, 196, 4491.
152 M. Sugawara, M. Ohno and K. Matsuki, J. Mater. Chem., 1997,
7, 833.
153 E. Rı́os, H. Reyes, J. Ortiz and J. L. Gautier, Electrochim. Acta,
2005, 50, 2705.
This journal is c The Royal Society of Chemistry 2012
View Article Online
154 M. D. Koninck, S. C. Poirier and B. Marsan, J. Electrochem.
Soc., 2006, 153, A2103.
155 V. Nikolova, P. Iliev, K. Petrov, T. Vitanov, E. Zhecheva,
R. Stoyanova, I. Valov and D. Stoychev, J. Power Sources, 2008,
185, 727.
156 F. Y. Cheng, J. Shen, B. Peng, Y. D. Pan, Z. L. Tao and J. Chen,
Nat. Chem., 2010, 3, 79.
157 K. Miyazaki, K. Kawakita, T. Abe, T. Fukutsuka, K. Kojima
and Z. Ogumi, J. Mater. Chem., 2011, 21, 1913.
158 M. Yuasa, M. Nishida, T. Kida, N. Yamazoe and K. Shimanoe,
J. Electrochem. Soc., 2011, 158, A605.
159 T. Lippert, M. J. Montenegro, M. Döbeli, A. Weidenkaff,
S. Müller, P. R. Willmott and A. Wokaun, Prog. Solid State
Chem., 2007, 35, 221.
160 A. Garsuch, A. Panchenko, C. Querner, A. Karpov, S. Huber and
R. Oesten, Electrochem. Commun., 2010, 12, 1642.
161 W. Zhou, J. Sunarso, Z. G. Chen, L. Ge, J. Motuzas, J. Zou,
G. X. Wang, A. Julbe and Z. H. Zhu, Energy Environ. Sci., 2011,
4, 872.
162 L. Malavasi, C. A. J. Fisher and M. S. Islam, Chem. Soc. Rev.,
2010, 39, 4370.
163 H. B. Wang, F. Y. Cheng, Z. L. Tao, J. Liang and J. Chen,
Chem. J. Chinese. Univ., 2011, 32, 595.
164 J. S. Lee, T. Lee, H. K. Song, J. Cho and B. S. Kim,
Energy Environ. Sci., 2011, 4, 4148.
165 A. Débart, J. L. Bao, G. Armstrong and P. G. Bruce, J. Power
Sources, 2007, 174, 1177.
166 A. Débart, A. J. Paterson, J. L. Bao and P. G. Bruce, Angew. Chem.,
Int. Ed., 2008, 47, 4521.
167 H. Cheng and K. Scott, J. Power Sources, 2010, 195, 1370.
168 A. K. Thapa, K. Saimen and T. Ishihara, J. Electrochem. Soc.,
2010, 13, A165.
169 F. P. Hu, X. G. Zhang, F. Xiao and J. L. Zhang, Carbon, 2005,
43, 2931.
170 Y. Y. Liang, Y. G. Li, H. L. Wang, J. G. Zhou, J. Wang,
T. Regier and H. J. Dai, Nat. Mater., 2011, 10, 780.
171 R. Bashyam and P. Zelenay, Nature, 2006, 443, 63.
172 H. Tributsch, Electrochim. Acta, 2007, 52, 2302.
173 C. W. B. Bezerra, L. Zhang, K. Lee, H. S. Liu, A. L. B. Marques,
E. P. Marques, H. J. Wang and J. J. Zhang, Electrochim.
Acta, 2008, 53, 4937.
174 E. B. Easton, R. Yang, A. Bonakdarpour and J. R. Dahn,
Electrochem. Solid-State Lett., 2007, 10, B6.
175 R. Z. Yang, K. Stevens and J. R. Dahn, J. Electrochem. Soc.,
2008, 155, B79.
176 E. B. Easton, A. Bonakdarpour, R. Z. yang, D. A. Stevens and
J. R. Dahn, J. Electrochem. Soc., 2008, 155, B547.
177 M. Lefèvre, E. Proietti, F. Jaouen and J. P. Dodelet, Science,
2009, 324, 71.
178 R. R. Chen, H. X. Li, D. Chu and G. F. Wang, J. Phys. Chem. C,
2009, 113, 20689.
179 G. Wu, K. L. More, C. M. Johnston and P. Zelenay, Science,
2011, 332, 443.
180 Q. G. He, X. F. Yang, X. M. Ren, B. E. Koel, N. Ramaswamy,
S. Mukerjee and R. Kostecki, J. Power Sources, 2011, 196,
7404.
181 F. Jaouen, E. Proietti, M. Lefèvre, R. Chenitz, J. P. Dodelet, G. Wu,
H. T. Chung, C. M. Johnston and P. Zelanay, Energy Environ. Sci.,
2011, 4, 114.
182 Z. Chen, J. Y. Choi, H. J. Wang, H. Li and Z. W. Chen, J. Power
Sources, 2011, 196, 3673.
183 S. S. Zhang, X. M. Ren and J. Read, Electrochim. Acta, 2011,
56, 4544.
184 J. S. Guo, H. X. Li, H. He, D. Chu and R. R. Chen, J. Phys.
Chem. C, 2011, 115, 8491.
185 M. Lefèvre, J. P. Dodelet and P. Bertrand, J. Phys. Chem. B,
2005, 109, 16718.
186 M. Kobayashi, H. Niwa, Y. Harada, K. Horiba, M. Oshima,
H. Ofuchi, K. Terakura, T. Ikeda, Y. Koshigoe, J. I. Ozaki,
S. Miyata, S. Ueda, Y. Yamashita, H. Yoshikawa and
K. Kobayashi, J. Power Sources, 2011, 196, 8346.
187 J. Chen, W. M. Zhang, D. Officer, G. F. Swiegers and
G. G. Wallace, Chem. Commun., 2007, 3353.
188 A. Trojánek, J. langmaier, J. Šebera, S. Záliš, J. M. Barbe,
H. H. Girault and Z. Samec, Chem. Commun., 2011, 47, 5446.
Chem. Soc. Rev., 2012, 41, 2172–2192 2191

189 B. Winther-Jensen, O. Winther-Jensen, M. Forsyth and
D. R. MacFarlane, Science, 2008, 321, 671.
190 S. Lee, S. Zhu, C. C. Milleville, C. Y. Lee, P. Chen, K. J. Takeuchi,
E. S. Takeuchi and A. C. Marschilok, Electrochem. Solid-State
Lett., 2010, 13, A162.
191 H. S. Liu, Z. Shi, J. L. Zhang, L. Zhang and J. J. Zhang,
J. Mater. Chem., 2009, 19, 468.
192 H. S. Oh, J. G. Oh, B. Roh, I. Hwang and H. Kim, Electrochem.
Commun., 2011, 13, 879.
193 S. S. Zhang, D. Foster and J. Read, J. Power Sources, 2010,
195, 1235.
Published on 17 January 2012. Downloaded by Northeastern University on 21/05/2013 03:34:00.
194 A. Kraytsberg and Y. Ein-Eli, J. Power Sources, 2011, 196, 886.
195 S. W. Eom, C. W. Lee, M. S. Yun and Y. K. Sun, Electrochim.
Acta, 2006, 52, 1592.
196 S. S. Sandhu, J. P. Fellner and G. W. Brutchen, J. Power Sources,
2007, 164, 365.
197 R. E. Williford and J. G. Zhang, J. Power Sources, 2009,
194, 1164.
198 J. Xiao, D. Wang, W. Xu, D. Wang, R. E. Williford, J. Liu and
J. G. Zhang, J. Electrochem. Soc., 2010, 157, A487.
199 P. Albertus, G. Girishkumar, B. McCloskey, R. S. Sánchez-Carrera,
B. Kozinsky, J. Christensen and A. C. Luntz, J. Electrochem. Soc.,
2011, 158, A343.
200 Y. G. Wang, L. Cheng, F. Li, H. M. Xiong and Y. Y. Xia,
Chem. Mater., 2007, 19, 2095.
201 N. Fujiwara, M. Yao, Z. Siroma, H. Senoh, T. Ioroi and
K. Yasuda, J. Power Sources, 2011, 196, 808.
202 J. Zhang, W. Xu and W. Liu, J. Power Sources, 2010, 195, 7438.
203 S. D. Beattie, D. M. Manolescu and S. L. Blair, J. Electrochem.
Soc., 2009, 156, A44.
204 W. H. Zhu, B. A. Poole, D. R. Cahela and B. J. Tatarchuk,
J. Appl. Electrochem., 2003, 33, 29.
2192 Chem. Soc. Rev., 2012, 41, 2172–2192
View Article Online
205 A. Kumar, F. Ciucci, A. N. Morozovska, S. V. Kalinin and
S. Jesse, Nat. Chem., 2011, 3, 707.
206 M. S. Islam and P. R. Slater, MRS Bull., 2011, 34, 935.
207 F. Y. Cheng, J. Liang, Z. L. Tao and J. Chen, Adv. Mater., 2011,
23, 1695.
208 F. A. Armstrong and J. Hirst, Proc. Natl. Acad. Sci. U. S. A.,
2011, 108, 14049.
209 J. Rossmeisl, K. Dimitrievski, P. Siegbahn and J. K. Nørskov,
J. Phys. Chem. C, 2007, 111, 18821.
210 D. R. Rolison, J. W. Long, J. C. Lytle, A. E. Fischer,
C. P. Phodes, T. M. McEvoy, M. E. Bourg and A. M. Lubers,
Chem. Soc. Rev., 2009, 38, 226.
211 M. Roberts, P. Johns, J. Owen, D. Brandell, K. Edstrom,
G. E. Enany, C. Guery, D. Golodnitsky, M. Lacey, C. Lecoeur,
H. Mazor, E. Peled, E. Perre, M. M. Shaijumon, P. Simon and
P. L. Taberna, J. Mater. Chem., 2011, 21, 9876.
212 W. Y. Li, C. S. Li, C. Y. Zhou, H. Ma and J. Chen, Angew.
Chem., Int. Ed., 2006, 45, 6009.
213 H. Ma, C. S. Li, Y. Su and J. Chen, J. Mater. Chem., 2007,
17, 684.
214 C. S. Li, W. Q. Ji, J. Chen and Z. L. Tao, Chem. Mater., 2007,
19, 5812.
215 M. Minakshi, D. Appadoo and D. E. Martin, Electrochem.
Solid-State Lett., 2010, 13, A77.
216 D. Aurach, J. Power Sources, 2000, 89, 206.
217 N. S. Choi, Y. M. Lee, K. Y. Cho, D. H. Ko and J. K. Park,
Electrochem. Commun., 2004, 6, 1238.
218 D. Zhang, R. S. Li, T. Huang and A. S. Yu, J. Power Sources,
2010, 195, 1202.
219 Y. Shimonishi, T. Zhang, N. Imanishi, D. Im, D. J. Lee,
A. Hirano, Y. Takeda, O. Yamamoto and N. Sammes,
J. Power Sources, 2011, 196, 5128.
This journal is c The Royal Society of Chemistry 2012