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Rechargeable lithium–air batteries: a perspective

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Cite this: J. Mater. Chem. A, 2016, 4,

14050
Kyu-Nam Jung,a Jeonghun Kim,b Yusuke Yamauchi,b Min-Sik Park,*c
Jong-Won Lee*a and Jung Ho Kim*b

Lithium–air battery (LAB) technology is currently being considered as a future technology for resolving
energy and environmental issues. During the last decade, much effort has been devoted to realizing
state-of-the-art LABs, and remarkable scientific advances have been made in this research field.
Although LABs possess great potential for efficient energy storage applications, there are still various
technical limitations to be overcome before the full transition. It has been well recognized that the
battery performance of LABs is mainly governed by the electrochemical reactions that occur on the
surface of the cathode. Thus, the rational design of highly reliable cathodes is essential for building high-
Received 31st May 2016
Accepted 16th August 2016
performance LABs. In this respect, we introduce recent advances in the development of LABs,
particularly focusing on the cathodes based on a fundamental understanding of Li–O2 electrochemistry.
DOI: 10.1039/c6ta04510c
Furthermore, we review the remaining technical challenges in order to formulate a strategy for future
www.rsc.org/MaterialsA research and consolidate Li–O2 electrochemistry for successful implementation of LABs in the near future.

1. Introduction
a
New and Renewable Energy Research Division, Korea Institute of Energy Research, 152
Gajeong-ro, Yuseong-gu, Daejeon 34129, Republic of Korea. E-mail: jjong277@kier.re.
Energy storage technologies have attracted great interest as
kr sustainable solutions to the energy crisis and environmental
b
Institute for Superconducting and Electronic Materials (ISEM), Australian Institute for concerns in modern society.1,2 In recent years, much of our
Innovative Materials (AIIM), University of Wollongong, North Wollongong, NSW 2500, research focus has been on developing efficient electrochemical
Australia. E-mail: jhk@uow.edu.au energy storage systems based on rechargeable batteries.3–7 The
c
Department of Advanced Materials Engineering for Information and Electronics,
success of rechargeable lithium-ion batteries (LIBs) has led to
Kyung Hee University, 1732 Deogyeong-daero, Giheung-gu, Yongin 17104, Republic
of Korea. E-mail: mspark@khu.ac.kr
a rapid paradigm shi in human life by accelerating

Dr. Kyu-Nam Jung is currently Dr. Jeonghun Kim received his

working as a Principal Research
Scientist at Korea Institute of
Energy Research (KIER). He
received his Ph.D. in 2007 in
Materials Science and Engi-
neering from Korea Advanced
Institute of Science and Tech-
nology (KAIST), and then he
worked as a Senior Research
Scientist at Samsung Electronics
(2007–2010) before joining KIER
in 2010. His research is
currently focused on the development of advanced functional
materials for electrochemical energy storage/conversion systems
including metal–air batteries, sodium-ion batteries and all-solid-
state batteries.
B.S. degree (2007) and Ph.D.
degree (2012) in the Dept. of
Chemical and Biomolecular
Engineering at Yonsei University
in Seoul, Korea. Until 2015, he
worked at Dongjin Semichem
Co., Ltd., in the Electronic
Materials Division, R&D Center
as a senior researcher for the
development of the synthesis,
production, and applications of
conductive polymers for elec-
tronic and energy devices. He is currently a postdoctoral fellow at
the Institute for Superconducting and Electronic Materials (ISEM),
Australian Institute for Innovative Materials (AIIM), University of
Wollongong, Australia. His major research interest is the design,
synthesis, and development of functional organic and inorganic
materials for electronic and energy storage applications.

14050 | J. Mater. Chem. A, 2016, 4, 14050–14068 This journal is © The Royal Society of Chemistry 2016
 View Article Online

Review Journal of Materials Chemistry A

technological advances in a wide variety of industries, particu-
larly with respect to portable electronic devices such as smart
phones and laptop computers. Nevertheless, the maximum
achievable energy density of LIBs is expected to be at most
250 W h kg 1, which limits their widespread use in newly
emerging applications that would require high-energy battery
systems, e.g., battery-powered electric vehicles (EVs).4–8 Among
the various rechargeable battery chemistries under develop-
ment, the lithium–air battery (LAB) is regarded as the most
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than those of current LIBs.9–19 Over the last decade, extensive
research on LAB technologies has been conducted, which has
greatly advanced our fundamental understanding of the Li–O2
reaction and the electrochemical aspects of materials used for
electrodes and electrolytes. There are still many problems that
need to be solved, however, including low capacity, poor rate-
capability, low round-trip efficiency (large voltage gaps between
discharging and charging), and short cycle life.9–19
The LAB is generally composed of a metallic Li anode

promising future technology for long-range EVs (>500 km), (negative electrode) and a porous cathode (oxygen electrode;
because its theoretical energy density is about ten times higher positive electrode) with different types of electrolytes.9–19 In

Prof. Yusuke Yamauchi received Dr. Jong-Won Lee is a Principal

his bachelor's degree (2003),
master's degree (2004), and
Ph.D. (2007) from the Waseda
University in Japan. Aer
receiving his Ph.D., he joined the
National Institute for Materials
Science (NIMS) as a permanent
staff to start his own research
group. In 2016, he joined the
University of Wollongong as
a full professor, and concur-
rently served as an honorary
principal investigator (PI) of the Mesoscale Materials Chemistry
group at NIMS. He also serves as a visiting professor at several
universities (Tianjin University in China, King Saud University in
Saudi Arabia, and Waseda University in Japan) and as an asso-
ciate editor of APL Materials published by the American Institute of
Physics (AIP). He has published more than 450 papers in inter-
national refereed journals with more than 15 000 citations (h-
index > 60). His major research interest is the tailored design of
inorganic nanostructured materials with various shapes and
compositions toward practical applications.
Research Scientist at Korea
Institute of Energy Research
(KIER) and an Associate
Professor at Korea University of
Science and Technology. He
received his Ph.D. (2005) in
Materials Science from Korea
Advanced Institute of Science
and Technology, and then he
worked as a Postdoctoral
Researcher (2005) and as
a Research Assistant Professor
(2006–2008) at the University of South Carolina (USA). He was an
R&D staff member (2008–2010) at Samsung Advanced Institute of
Technology before joining KIER in 2010. His current research is
focused on advanced functional materials for next-generation
energy storage/conversion systems.

Prof. Min-Sik Park is an assis- Prof. Jung Ho Kim is currently

tant professor in the Department
of Advanced Materials Engi-
neering for Information and
Electronics of Kyung Hee
University. He received his Ph.D.
at the University of Wollongong
(Australia) in 2008. As a visiting
student, he studied at the Tokyo
Institute of Technology (2007–
2008). Aer receiving his Ph.D.
in 2008, he was a research staff
member at the Samsung
Advanced Institute of Technology (2008–2010) and a managerial
researcher at the Korea Electronics Technology Institute (2010–
2016). His current research is focused on advanced materials for
energy storage systems such as lithium-ion batteries, lithium-ion
capacitors, and post-lithium systems for next-generation energy
storage.
Professor at the Institute for
Superconducting and Electronic
Materials (ISEM), Australian
Institute for Innovative Mate-
rials (AIIM), University of Wol-
longong, Australia. He received
his Bachelor's (1998), Master's
(2000), and Ph.D. (2005)
degrees from Sungkyunkwan
University, Korea. He has pub-
lished more than 200 papers in
international refereed journals.
He is currently acting as an editorial board member for Scientic
Reports (Nature Publishing Group). His major research interest is
the rational design of materials with one-, two-, and three-
dimensions towards energy storage and harvesting applications.

This journal is © The Royal Society of Chemistry 2016 J. Mater. Chem. A, 2016, 4, 14050–14068 | 14051

Journal of Materials Chemistry A
principle, oxygen (O2) supplied from ambient air serves as the
active material for the LAB, thereby providing a great benet in
terms of energy density over conventional LIBs. Different types
of LABs are currently being studied; most R&D activities have
been devoted to non-aqueous LAB designs with an organic,
aprotic electrolyte because of the higher energy density of this
type than that of the others.20–31 In this conguration, solid-state
products (mostly Li2O2) are formed as a result of electro-
chemical reactions between O2 and Li+ during discharging, and
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they decompose reversibly upon subsequent charging. A porous
cathode provides the reaction sites for electrochemically active
species (O2 and Li+) and stores the solid-state discharge prod-
ucts (Li2O2). Therefore, the storage capability and reversibility of
the LAB would be highly dependent on the nature of the elec-
trochemical reactions on the cathode surface, as well as the
materials and architecture of the cathode. In fact, the contin-
uous accumulation of solid Li2O2 species inside the porous
cathode results in a gradual reduction of the active surface area
over the course of discharging, causing premature battery
death. More importantly, carbon (the cathode material of
choice for current LABs) is quite vulnerable to parasitic reac-
tions with non-aqueous electrolytes and Li2O2, which results in
signicant degradation of the LAB's cyclability.22,24,32,33 To
resolve these confronting problems, it is crucial to understand
the fundamental aspects of electrochemical reactions in non-
aqueous electrolytes and to develop advanced cathodes for
robust, high-performance LABs. In this review, we briey
introduce the technical challenges facing the development of
non-aqueous LABs and provide an update of the fundamental
science of oxygen electrochemistry in LABs. Then, we present
recent, promising approaches to improve the electrochemical
performance of the cathode for LABs: (i) synthesis of nano-
structured porous carbon and the modication of its porous
architecture for capacity improvement, and (ii) technical strat-
egies to mitigate the problems associated with carbon insta-
bility and to design alternative cathodes with improved stability
and reversibility. Given that several review articles on cathode
electrocatalysts already exist, here, we provide a focused review
that mainly deals with recent advances in nanostructured
porous cathodes based on carbon and non-carbon materials.
Finally, further discussion will be provided on the future pros-
pects of LABs. We believe that this review will serve as a valuable
reference, which can provide guidelines for developing
commercially viable LAB systems as the power source for next-
generation EVs.
2. Technical challenges of lithium–air
batteries
The discovery and initial development of LABs were motivated
by their extremely high theoretical energy density. The concept
of Li–O2 chemistry was rst proposed by Littauer et al.34–36 in
1976, but it received little attention until a rechargeable LAB
system with a non-aqueous electrolyte was demonstrated by
Abraham et al.37 in 1996. As schematically illustrated in Fig. 1,
an LAB is composed of a metallic Li anode, a porous cathode,
14052 | J. Mater. Chem. A, 2016, 4, 14050–14068
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Review
and an electrolyte between the two electrodes.9–19 During dis-
charging, Li+ generated via the Li oxidation migrates across the
electrolyte toward the cathode, where Li+ combines with O2
from the atmosphere and electrons from the external circuit,
forming Li–O compounds. When the LAB is recharged, Li atoms
and O2 are regenerated as a result of the reverse reaction, and
then, the O2 is released from the battery (open system) or is
retained in a reservoir (closed system).13,38 There are four cell
congurations of LABs under development, which are catego-
rized according to the types of electrolytes: (i) non-aqueous
(aprotic), (ii) aqueous, (iii) hybrid, and (iv) solid electro-
lytes.9,16,19,39–43 A full description of the four congurations is
beyond the scope of this review; more detailed information can
be found elsewhere.9,16,17,19 Among them, the non-aqueous LAB
is the most advantageous system because it has the ability to
deliver the highest energy density and to sustain reversible
cycling.13,18 The theoretical specic energy densities of the non-
aqueous LAB (calculated based on the weights and volumes of
active materials) are expected to be 3458 W h kg 1 (gravimetric)
and 3445 W h L 1 (volumetric), which exceed those of currently
available LIBs.13,16 In this regard, we will focus primarily on the
non-aqueous LAB system in the following sections. Undoubt-
edly, there are still many technical challenges that need to be
addressed, as summarized in Fig. 1. The key challenges facing
the development of non-aqueous LABs are highlighted as
follows:
(a) Decomposition of non-aqueous electrolytes
To date, carbonate-based electrolytes have been commonly used
for LIBs, but unfortunately, they are unstable against super-
oxide radicals (O2 ) generated during LAB operation.22,44,45 In
this respect, other candidates based on ethers,21,23,27,32,46–48
sulfones,49,50 sulfoxides,51–53 and ionic liquids54–57 have been
explored as alternative electrolytes for LABs. A truly stable
electrolyte is yet to be demonstrated, however.
(b) Growth of Li dendrites and parasitic reaction of Li with
H2O
The degradation of Li metal associated with the dendritic
growth during the repeated Li dissolution/deposition process
still remains an open problem.13,18,58,59 It is also essential to
prevent undesirable reactions of Li with the electrolyte and
impurities (e.g., H2O) present in ambient air.60,61
(c) Slow kinetics of oxygen reactions and degradation of
carbon cathodes
The cathode is a core component of LABs, which offers active
sites for electrochemical reactions, i.e., Li2O2 formation (oxygen
reduction reaction: ORR) and Li2O2 decomposition (oxygen
evolution reaction: OER) during discharging and charging,
respectively.9–19 The cathode also plays the important role of
accommodating the discharge products. In addition to lower-
than-expected capacity, however, LAB cathodes show poor
round-trip efficiency and rate-capability, largely due to the
sluggish kinetics of the ORR and OER. As will be discussed in
detail in this review, furthermore, carbon decomposition in the
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Fig. 1 Major technical challenges for the rechargeable Li–air battery.
presence of Li2O2 is known to be one of the main causes of poor
cycling performance.22,24,32,33 Considerable efforts are currently
being put into resolving the technical issues summarized in
Fig. 1. It is obvious that the realization of commercial LAB
technology would be impossible without having a fundamental
understanding of Li–O2 electrochemistry on the cathode, which
will be discussed in the following section.
3. Oxygen electrochemistry in a non-
aqueous lithium–air battery
In-depth insights into the electrochemical reaction mecha-
nisms will help us to design and construct highly active and
stable cathodes for LABs. In this section, therefore, we review
the previous reports that elaborate the mechanisms of the
electrochemical oxygen reactions (ORR and OER) on the
cathode and clarify the physical, chemical, and electrochemical
factors limiting cathode performance.
3.1. Reaction pathways of oxygen reduction and oxidation
It is generally agreed that the dominant discharge product in
the cathode of the non-aqueous LAB is lithium peroxide (Li2O2)
rather than lithium oxide (Li2O).21,23,32 Based on a computa-
tional study, Radin et al.62 proposed that stable Li2O2 surfaces
are half-metallic, unlike Li2O with both non-metallic and non-
magnetic properties. Such a distinctive characteristic makes
Li2O2 the most desirable discharge product of the non-aqueous
LAB. Although there are some arguments over the reaction
mechanism of Li and O2 in the discharge process, the formation
of Li2O2 is known to proceed via a one-electron transfer reaction
to form the superoxide species (O2 ), followed by
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Journal of Materials Chemistry A
disproportionation of LiO2 to Li2O2 (eqn (3)) or another one-
electron-transfer reaction (eqn (4)) as follows:32,63–67
O2 + e / O2 (1)
O2 + Li+ / LiO2 (ads) (2)
2LiO2 / Li2O2 + O2 (3)
LiO2 + Li+ + e / Li2O2 (4)
This reaction pathway has been experimentally conrmed by
in situ surface enhanced Raman spectroscopy (SERS) and
differential electrochemical mass spectroscopy (DEMS). During
charging, on the other hand, Li2O2 undergoes direct decom-
position to O2 without forming LiO2(ads) intermediates:63,64,66
Li2O2 / 2Li+ + 2e + O2 (5)
Recent studies31,68 have suggested that the chemical nature
of discharge products may be dependent on the electrolyte
additives and catalysts. Liu et al.31 demonstrated a highly effi-
cient LAB comprising a rGO electrode, DME-based electrolyte,
and LiI additive (acting as a redox mediator). They claimed that
the dominant discharge product is LiOH, which can be easily
oxidised by I3 at potentials as low as 3 V vs. Li/Li+ during
charging. Together with H2O present in the electrolyte, LiI
modies the reaction pathways so as to induce the formation of
LiOH : O2 which is rst reduced to LiO2 on the rGO surface, and
then, LiO2 combines with H2O to form LiOH with the action of
LiI. Lu et al.68 reported that crystalline LiO2 can be stabilised in
LABs by using an Ir–rGO electrode. The LiO2 formed in the LAB
can be reversibly charged and discharged with low over-
potentials and the formation of crystalline LiO2 is attributed to
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Journal of Materials Chemistry A Review

the Ir nanoparticle catalysts that act as a template for the
nucleation and growth of LiO2.
Unfortunately, in most cases, the discharge process of the
LAB is accompanied by electrolyte decomposition, resulting in
the formation of parasitic products.22,23,44,69–71 Carbonate-based
electrolytes were initially used as solvents for non-aqueous
LABs; however, it was proved that the carbonate-based electro-
lytes can easily decompose to high molecular weight products,
such as lithium alkyl carbonates, C3H6(OCO2Li)2, Li2CO3,
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(Fig. 2(a)–(c)). The additional transmission electron microscopy
(TEM) analysis conrmed that the toroidal particles have
a highly crystalline microstructure with the Li2O2 (0001) facet
normal to the axis of the toroid. The average crystallite sizes of
Li2O2 were measured to be approximately 10–15 nm. Moreover,
computational studies reported by Radin et al.62 and Mo et al.79
have suggested that (0001) is the predominant surface in the
equilibrium Wulff construction of Li2O2 crystallites.
In general, the charge process turned out to consist of two

HCO2Li, and CH3CO2Li, at the cathode surface, because the different reactions: a delithiation process with a low over-
carbonates are highly susceptible to nucleophilic substitution potential at the surface, followed by a bulk oxidation process
by O2 .22,23,44,69–71 During charging, signicant CO2 evolution (disproportionation) with a higher overpotential, as proposed
was detected as a result of the electrochemical decomposition by Lu et al.80 (Fig. 2(d)). In a recent study, Gallant et al.81 studied
of carbonate species, as evidenced by in situ DEMS analysis.22,23 the effects of Li2O2 morphologies on the charging behaviour of
Non-carbonate electrolytes, such as tetraethylene glycol the LAB and found that relatively small disk-like particles
dimethyl ether (TEGDME),27,46 1,2-dimethoxyethane (DME),23,32 exhibit a slower rise in the charge overpotential compared with
dimethyl sulfoxide (DMSO),51–53 and tetramethylene sulfone
(TMS),49,50 have been extensively investigated as alternatives for
LABs, due to their higher chemical stability in the presence of
the O2 radical compared to carbonates. In practice, the better
stability of these electrolytes promotes more reversible forma-
tion and decomposition of Li2O2 at the cathode surface, as
conrmed by various analytical studies.72–74 It should be noted,
however, that Trahan et al.52 demonstrated that when DMSO-
based electrolytes are used with carbon cathodes, LiOH is the
major crystalline by-product. The LiOH formation is attributed
not only to the water contamination, but also to the water
generated via a side reaction between LiO2 and DMSO. This
indicates that ether- and sulfone-based electrolytes may not be
suitable for LABs, which is stimulating interest in the develop-
ment of more stable electrolytes.

3.2. Effects of cell operating conditions

A unique aspect of Li–O2 electrochemistry is the formation of
a solid discharge product (Li2O2) on the cathode surface. The
chemical and morphological properties of Li2O2 formed on any
cathode surface are fundamentally important for determining
the electrochemical performance of LABs, such as capacity,
round-trip efficiency (overpotentials), rate-capability, and cycle
life. In this respect, many researchers have focused on the
mechanism of Li2O2 formation and its impacts on the electro-
chemical behaviour of the LAB.75–78 Adams et al.76 showed the
strong inuence of the applied discharge current on the
morphology and crystallinity of Li2O2 during LAB operation. At
a low current density (5 mA cm 2), the formation of large-scale
toroidal nanocrystalline Li2O2 aggregates was evident. At
a higher current density (100 mA cm 2), on the other hand, Li2O2
tends to have a lm-like morphology and much less crystal-
linity, so that it can be easily oxidized at lower overpotentials,
i.e., improved round trip efficiency. Also, Mitchell et al.77 probed Fig. 2 SEM micrographs of (a) disc- and (b) toroid-shaped Li2O2
the mechanistic details of Li2O2 formation during discharging. particles formed on carbon nanotube (CNT) electrodes discharged at
According to their report, as the discharge process proceeds, 10 mA gC 1 to gravimetric capacities of 200 mA h gC 1 and
1400 mA h gC 1, respectively. (c) Schematic illustration of shape
Li2O2 particles are initially formed as 10 nm thick, stacked
evolution of Li2O2 particles from disc to toroid with increasing size.
plates on the carbon nanotube cathode, and then, the plates Reprinted with permission from ref. 77. (d) Diagrammatic representa-
become splayed out, followed by additional plate nucleation, tion of the proposed reaction mechanism of the OER process.
which nally causes the formation of toroidal Li2O2 particles Reprinted with permission from ref. 80.

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large toroidal particles. The reduced overpotential was ascribed
to the larger surface-to-volume ratio: i.e., a larger fraction of
surface delithiation can lower the overall overpotential. Simi-
larly, Hu et al.82 examined the impact of the Li2O2 particle size
on the charging performance of the LAB by charging Li2O2
particles with different particle sizes (160 and 600 nm) that were
pre-loaded on the carbon cathode. As supposed, the smaller
Li2O2 particles showed a lower potential plateau for charging,
resulting from the reduced electrode polarization and enhanced
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kinetics of Li2O2 oxidation.
It is worth noting that most studies of LABs have been con-
ducted using pure oxygen.13,83 From the practical viewpoint,
however, LABs should be able to operate with ambient air that
may contain impurities such as CO2 and H2O. The effects of CO2
on the electrochemical behaviour of an LAB with a DME elec-
trolyte were studied by Gowda et al.84 The authors discovered
the important fact that CO2 spontaneously reacts with Li2O2 to
form Li2CO3 during discharging. On subsequent charging, CO2
evolution occurs from Li2CO3 at potentials of >4.0 V vs. Li/Li+,
which are much higher than those for O2 evolution from Li2O2
(3.0–3.5 V vs. Li/Li+). As a consequence, the CO2 contamina-
tion would cause the LABs to have poor round-trip efficiency.
Lim et al.85 also investigated the reaction mechanisms of Li–O2/
CO2 cells using quantum mechanical simulations combined
Fig. 3 (a) Schematic illustration of the growth mechanism of toroid-shaped Li2O2 in the presence of water. (b) Comparison of toroid-shaped
Li2O2 particle sizes calculated based on the proposed particle growth model under electrolyte containing 1000 ppm and 4000 ppm of water.
Reprinted with permission from ref. 86.
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Journal of Materials Chemistry A
with experimental verication. According to their results, the
electrolyte solvation strongly inuences the reaction pathway
for the nal discharge product by altering the surface potential
energy: namely, the highly dielectric DMSO is favourable for
electrochemical activation of CO2 to form Li2CO3, while DME
with a low dielectric property would form Li2O2 as a major
discharge product.
Aetukuri et al.86 suggested that the morphology of Li2O2 is
strongly dependent on the H2O content in the electrolyte
(Fig. 3). At a high H2O content (4000 ppm), toroid-like Li2O2
products were formed in the high current range (1 mA), whereas
at a low H2O content (<30 ppm), the formation of Li2O2 toroids
was not detectable, even at quite low currents (50 mA). Their
experimental and simulation results showed that the H2O
impurity with a high Gutmann acceptor number (55) triggers
the dissolution process by solvating O2 from LiO2(ads). The
soluble O2 species undergoes a subsequent reaction on
a growing Li2O2 toroid through the “solution mechanism”
(Fig. 3(a)). Moreover, increasing the H2O content in the elec-
trolyte induces high discharge capacity due to the formation of
larger toroidal Li2O2 products (Fig. 3(b)), although it causes an
increase in the charging potential, resulting in low round-trip
efficiency and poor cyclability of the LABs. Very recently, the
benzoquinone-based additive was reported to effectively
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Journal of Materials Chemistry A
promote the solution phase formation of Li2O2 particles, while
suppressing the direct formation of Li2O2 lms on the cathode
surface.87
4. Oxygen electrodes for non-
aqueous lithium–air batteries
4.1. Nanostructured porous carbon
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Since the formation of poorly conducting solid discharge
products (e.g., Li2O2) occurs in the cathode, rational design of
the cathode is essential for building robust and high-perfor-
mance LABs. The specic surface area, pore volume, pore size,
and electrical conductivity of cathodes are generally regarded as
the predominant factors for determining the electrochemical
performance of LABs.88,89 In this respect, much attention has
been devoted to the development of nanostructured carbon
materials that have large surface areas and well-dened pore
structures for practical use in LABs. Over the past several
decades, various carbon materials have attracted particular
attention for electrochemical energy storage systems as elec-
trode materials, conductive additives, and catalysts, owing to
their advantages over other candidates, for example, large
surface area, high electrical conductivity, high chemical
stability, and low cost.90 For rechargeable LAB technology, the
promising characteristics of carbon make carbon materials
viable candidates for cathode materials–carbon is the electrode
material of choice for current LABs.16,18,91 Various nano-
structured carbon materials have been explored as potential
cathodes for LABs. In this section, we review the recent progress
in the development of various nanostructured carbon materials
and their potential use as cathode materials for LABs. Moreover,
the remaining technical issues arising from carbon instability
are discussed.
4.1.1. Structural modications of commercially available
carbon materials. At the early stage of research, commercially
available carbon materials were employed as cathodes for LABs.
For example, carbon blacks (CBs), which are derived from heavy
petroleum products, have been used as popular cathode mate-
rials, thanks to their three-dimensional (3D) network structure
that features high surface area and excellent electrical conduc-
tivity.92–94 Even though these characteristics of CBs are advan-
tageous for facilitating electrochemical redox reactions, the
practical use of CBs would be limited for large-scale LABs, due
to their relatively low capacity, the difficulty of electrode fabri-
cation, and their poor dimensional stability.
In the pursuit of nding highly efficient carbon materials,
researchers have focused on the correlation between the phys-
icochemical properties and the electrochemical performance of
carbon.16,92,95 Previous reports have revealed that a large pore
volume and a uniform pore size distribution are crucial for
improving the electrochemical performance of LABs.92–94
Therefore, the most fruitful development direction for carbon
materials would be optimizing their pore structures to facilitate
transport of oxygen and Li+ to the active surface of the cathode.
In this respect, the potential candidates include carbon nano-
tubes (CNTs) or carbon nanobers (CNFs), which have
14056 | J. Mater. Chem. A, 2016, 4, 14050–14068
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Review
extraordinary mechanical and electrical properties. As proved
by Mitchell et al.,94 CNTs or CNFs exhibit greatly improved
reversible capacity and cycling performance due to their high
utilization of carbon mass and void volume for Li2O2 formation.
Moreover, the one-dimensional (1D) structure of CNTs or CNFs
allows fast charge transfer and excellent dimensional stability
during cycling.96–99 In addition, these types of carbon materials
can be used as a framework for constructing composite struc-
tures with other functional materials (e.g., nanocatalysts).
Nevertheless, the electrochemically active surface areas of CNTs
or CNFs are relatively smaller than those of other candidates
because they can be easily agglomerated. To overcome these
problems, additional structural modications or chemical
treatments are necessary.16 More recently, two-dimensional (2D)
carbon materials, well-known as graphene or reduced graphene
oxide (rGO), have received great attention as potential cathodes
for LABs.100–103 The electrochemical properties of graphene or
rGO can be tuned by control of the assembly of individual
graphene sheets. For successful implementation, it is important
to prevent re-stacking of the individual graphene sheets to
maintain their large surface area and controlled pore
structure.100,102,103
Bearing this in mind, researchers have focused on structural
modications of these commercially available multi-scale
carbon materials.16,25,103,104 One of the most effective approaches
is constructing hierarchical 3D structures with large surface
areas and pore volumes by assembling carbon materials. Xiao
et al.25 synthesized hierarchically porous graphene consisting of
an unusual arrangement of functionalized graphene sheets and
reported its excellent electrochemical activity as a cathode
material for LABs. Without decoration by any catalysts, it
delivered an exceptionally high capacity of 1500 mA h g 1.
Alternatively, nanopores can be incorporated into the carbon
materials in various ways to increase the surface area and pore
volume. Even if there are slight differences, Sun et al.104
proposed porous graphene nanoarchitectures in which abun-
dant nanopores (25 nm in size) were successfully integrated
into graphene sheets (Fig. 4). By employing Ru nanocatalysts on
the porous graphene architecture, high capacity and long cycle
life LABs were achieved with good performance up to 200
cycles.104 Apart from these structural modications, heteroatom
(B, N, S, P, etc.) doping into carbon is considered as an effective
way to improve the round-trip efficiency of LABs, which is an
important challenge for their practical use.96,105–107
4.1.2. Design and synthesis of advanced carbon materials.
At present, much effort has been made to look for a new class of
porous carbon materials, which would be favourable for
boosting redox reactions in LABs. The recent progress in porous
carbon materials has been opening up new directions and
strategies to develop highly reliable and sustainable cathodes
for LABs. It is well recognized that the capacity of an LAB greatly
depends on the accessible mesopores (2–50 nm in size),
whereas micropores <2 nm in size are too small to support Li2O2
deposition during discharging.18,54,108 It is thus essential to
incorporate abundant mesopores into carbon materials to
improve their electrochemical performance. In this respect,
various carbon materials with unique porous architectures have
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Fig. 4 (a) Schematic diagram of the synthesis process for a Ru-
decorated porous graphene nanoarchitecture. (b) SEM and (c) TEM
micrographs of Ru nanocrystal-functionalized porous graphene, with
the inset in (c) showing the corresponding electron diffraction pattern.
Reprinted with permission from ref. 104.
been designed and synthesized, and their feasibility has been
thoroughly examined in non-aqueous LABs.91,94,109–112
As a potential cathode material for LABs, 3D ordered meso-
porous (3DOm) carbon with an open structure has been devel-
oped by Xie et al. (Fig. 5).109 The specic surface area and pore
size of 3DOm carbon can be independently tuned to facilitate
electrochemical redox reactions as well as securing excellent
dimensional stability. Their results demonstrated that the
3DOm carbon enables preferential Li2O2 deposition within the
mesopores, which results in high reversible capacity. A similar
approach has been proposed by Gou et al.110 using ordered
hierarchical mesoporous/macroporous carbon. The ordered
mesoporous channels and hierarchical porous structures facil-
itated electrolyte uptake as well as Li+ diffusion. Indeed, suffi-
cient free space allowed the reversible formation and
decomposition of Li2O2, leading to enhanced electrochemical
performance of the LAB.16 Another potential candidate is metal–
organic frameworks (MOFs), which provide a wide range of
surface areas and diverse pore structures, depending on the
metal ions and linkers used in the synthesis.91,111–114 Wu et al.112
prepared various types of MOFs with different pore structures
and examined their electrochemical performance as cathode
materials for LABs (Fig. 6). They suggested that the robustness
of MOFs avoids the self-aggregation oen encountered by
nanostructured carbon materials, thereby maintaining elec-
trode integrity. In addition, the intrinsic open metal sites
formed in the MOFs can improve the accessibility of active
species. These are benecial for achieving a high reversible
capacity and long-term cycling performance of LABs.91,112
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By precisely engineering the porous structure of carbon
materials, the capacity and reversibility of LABs can be effec-
tively enhanced, and this endeavour is still continuing due to
the importance of novel cathode designs for developing high-
performance LABs.16,31,115 Despite all of the efforts presented
above, there is another technical issue that needs to be
addressed for further improvement of carbon materials for
LABs; namely, carbon instability.
4.1.3. Carbon instability. Although carbon exhibits great
potential as a cathode material for LABs, the chemical stability
issues for carbon during the discharge–charge process are
considered to be a major impediment to realization of robust
and stable cathodes.16,91 While Li2O2 is the major product
formed during discharging, many researchers have reported
experimental results showing that Li2CO3 also forms during the
operation of LABs with carbon cathodes.22,24,32,33 Based on the
results of X-ray photoelectron spectroscopy (XPS) and isotopi-
cally labelled DEMS, McCloskey et al.24 demonstrated that the
formation of Li2CO3 during the discharge–charge process in an
ether-based electrolyte is attributable to the side reactions of
Li2O2 with the electrolyte and with the carbon cathode. From
a quantitative analysis of the CO2 species evolved during
charging, they reported that 12CO2 is evolved due to the elec-
trolyte decomposition in the lower charging potential region
(3.0–4.0 V vs. Li/Li+), while 50% of 13CO2 is evolved from the
Li213CO2 present at the interface between carbon and Li2O2 in
the higher charge potential range (4.0–4.5 V vs. Li/Li+). These
results imply that carbon is not stable and reacts with Li2O2
under typical operation conditions for LABs. Theoretical
predictions by the authors also suggested that the monolayer of
Li2CO3 that is formed at the interface between carbon and Li2O2
causes a 10–100-fold decrease in the exchange current density
(i.e., considerable interfacial resistance to charge transfer),
resulting in the higher charging potentials and lower round-trip
efficiency of the LABs.
Moreover, it was suggested that the instability of carbon is
strongly dependent on its surface structure and chemical
properties. With the help of in situ XPS measurements, Itkis
et al.116 proposed that the superoxide radicals formed on the
carbon cathode during discharging may react with carbon by
creating oxygenated surface functional groups and defects to
promote the formation of considerable epoxy groups and
carbonates on the carbon surface. This indicates that the
reduction of defects and functional groups on the carbon
surface could be a way to enhance carbon stability in LABs.
Thotiyl et al.33 proposed that the stability of carbon also
depends upon its hydrophobic or hydrophilic nature. By using
acid and Fenton's reagent combined with DEMS, they quanti-
ed CO2 generated by Li2CO3 oxidation and Li carboxylate
oxidation from the 13C cathode during discharging and
charging of LABs with DMSO and TEGDME electrolytes. They
demonstrated that carbon oxidatively decomposes to form
Li2CO3 in the presence of Li2O2 during charging at >3.5 V vs.
Li/Li+, since carbon promotes electrolyte decomposition. In
particular, it was suggested that hydrophilic carbon is more
prone to promote electrolyte decomposition compared with
hydrophobic carbon due to the higher density of surface
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Fig. 5 (a) Structural representation of 3DOm carbon and (b) schematic illustration of the formation of Li2O2 and accumulation of by-products on
3DOm carbons with different pore structures. (c) Cycling performance and (d) discharge–charge profiles of Li–O2 cells using 3DOm carbons
with different pore sizes. Reprinted with permission from ref. 109.
Fig. 6 (a) Schematic illustration of the Li–O2 battery with the MOF-
containing cathode. (b) Discharge profiles of Li–O2 cells constructed
using MOFs with diverse pore structures at a current density of
50 mA g 1. Reprinted with permission from ref. 112.
14058 | J. Mater. Chem. A, 2016, 4, 14050–14068
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functional groups such as C–O, COOH, and C–OH on the
surface of hydrophilic carbon. Due to the carbon stability
issues, replacing carbon with non-carbon materials may be
a potential strategy to improve the stability of the cathode in
LABs.
4.2. Novel approaches to designing stable and reversible
cathodes
Carbon is generally considered as a good cathode material in
LABs; however, it suffers from corrosion/oxidation at high
potentials and promotes electrolyte decomposition during
cycling. Therefore, it is imperative to nd alternative cathodes
to circumvent side reactions involving carbon-based materials.
To resolve this problem, two strategies have been widely
applied: one is surface modication of carbon by uniform
coating with stable non-carbon materials,109,117–126 and the other
is to design “carbon-free” cathodes.26,127–157 Both strategies can
effectively mitigate undesirable side reactions arising from
carbon instability, thus avoiding or reducing the formation of
by-products such as lithium carbonates.
4.2.1. Surface modication of carbon. In order to prevent
side reactions arising from carbon instability, there have been
many attempts to make the carbon surface more stable against
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chemical attack through surface modication of carbon with
metal oxides.109,117–122,124 As mentioned in the preceding section,
the defects and functional groups on the carbon surface can
provide the reaction sites for the formation of Li2CO3 and the
promotion of electrolyte decomposition. Thus, the deactivation
of defects and functional groups by stable oxides could be
a promising approach to enhance carbon stability under highly
oxidative conditions. Lu et al.117 reported a carbon cathode in
which surface defects were passivated with Al2O3 nanoparticles
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formed via atomic layer deposition (ALD). The porous carbon
powder (Super P) was surface-modied with ALD-deposited
Al2O3 nanoparticles, and subsequently, it was deposited with
a Pd nanocatalyst. The very low charging overpotential of 0.2 V
at a current density of 100 mA g 1 was achieved with the
surface-modied carbon cathode. The Al2O3 coating effectively
prevents the carbon oxidation and electrolyte decomposition,
and at the same time, the Pd nanocatalyst particles promote the
growth and formation of nanocrystalline Li2O2 with high elec-
tronic transport properties. In a similar way, ZnO-passivated
porous carbon was also fabricated by using the ALD tech-
nique,124 and CNT composites decorated with metal oxide
nanoparticles such as CoFe2O4 and NiFe2O4, (acting as both
electrocatalysts for the ORR/OER and defect deactivators) were
also proposed.120
Complete carbon passivation with a uniform coating layer is
helpful for completely blocking the active sites for parasitic
reactions. Jian et al.121 reported a core–shell-structured
CNT@RuO2 composite as a cathode for LABs (Fig. 7). Through
a simple sol–gel method, RuO2 shells with a thickness of 4 nm
were uniformly formed on the surfaces of the CNTs in the
cathode. The RuO2 shell could improve the chemical stability of
the CNT framework and showed good catalytic activities
towards the ORR and OER without sacricing the high elec-
tronic conductivity of CNTs. As shown in Fig. 7(e) and (f), the
CNT@RuO2 cathode showed a high specic capacity and
remarkably reduced charge potentials in comparison with the
CNT-only cathode, as well as excellent cyclability (>100 cycles) at
a high current density of 500 mA gtotal 1. Such improvements
are attributed to the suppression of contact between the CNTs
and the electrolyte and discharge product. Xie et al.109 also
proposed a porous 3DOm carbon cathode surface-passivated
with FeOx (Fig. 8). A thin FeOx layer with a thickness of 1.4 nm
was conformally deposited on the 3DOm carbon with a well-
dened mesoporous structure, followed by decoration with the
Pd nanocatalyst through ALD. The enhanced cycling perfor-
mance (68 cycles) of the Pd–FeOx–3DOm carbon compared with
that of pristine 3DOm carbon (13 cycles) is attributed to the
efficient protection of the carbon surface against chemical
attack, as well as the high catalytic activities of Pd and FeOx
towards the ORR and OER, respectively. In addition, the direct
growth of transition metal oxides with a hierarchical structure
on a carbon substrate such as ower-like-d-MnO2 on gra-
phene122 and NiCo2O4 nanowires on carbon cloth118,126 also can
be effective ways to protect the carbon surface to enhance the
stability of carbon cathodes in LABs, while increasing the active
surface areas.
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4.2.2. Carbon-free cathodes. Another promising strategy
for mitigating the side reactions associated with carbon insta-
bility in LABs is to develop carbon-free cathodes. Currently,
many researchers have focused on nding stable non-carbon
materials and designing multi-scale porous structures from
them to improve both capacity and reversibility. Various mate-
rials, such as noble metals,26,129,134,143,145,152–154 metal
oxides127,130,131,135–142,146–149,156/carbides132,150/nitrides128,133/suldes,157
and their composites,144,151 have been examined for their feasi-
bility as potential cathodes for LABs so far. For proper use,
a carbon-free cathode for LABs should possess the following
physical attributes in addition to chemical stability: (i) high
electrical conductivity for facilitating charge transport at the
interface and through the matrix; (ii) high specic surface area
for electrochemical redox reactions; (iii) optimized pore struc-
ture (macro, meso, and micro) and porosity for accommodating
the discharge product without blockage of reactants moving to
and from reactive sites; (iv) high catalytic activity towards the
ORR and OER, but no activity towards electrolyte decomposi-
tion during cycling; (v) low material cost. The cathode designs
may be divided into two categories: (i) conventional composite
cathode fabricated by coating or pressing a mixture of the active
material and binders onto a current collector; (ii) free-standing-
type cathode directly grown on a current collector without using
any binders.
4.2.2.1 Conventional composite electrode design. In general,
noble metals have high electrical conductivity and possess high
catalytic activities towards the ORR and OER in non-aqueous
electrolytes. Owing to these promising aspects, many
researchers have tried to use these materials as the main
constituent of carbon-free cathodes. The rst attempt was re-
ported by Peng et al.,26 who used a carbon-free nanoporous gold
(NPG) cathode combined with a DMSO-based electrolyte.
Although the reversible capacity was limited to 300 mA h g 1 at
500 mA g 1, the cell could retain 95% of original capacity aer
100 cycles. The stability and reversibility of the proposed system
were veried by Fourier transform infrared (FTIR) spectroscopy
and DEMS analysis, which showed O2 evolution at potentials
below 4.0 V vs. Li/Li+ without any evidence of CO2 evolution. In
situ visual observation of the Li–O2 reaction using atomic force
microscopy (AFM) revealed that, in addition to the high stability
of NPG itself, the low overpotentials of the corresponding LABs
were attributable to the formation of dense Li2O2 lms on the
NPG cathode due to its high O2 adsorption affinity and high
electrical conductivity, which can easily promote the decom-
position of the Li2O2 lm on charging.134 Aer that, Chen
et al.144 proposed a nanoporous metal/metal oxide hybrid
material with a core–shell structure as a carbon-free cathode for
LABs (Fig. 9(a)–(c)). Here, the nanoporous Au lm was rst
fabricated by a controlled de-alloying process in an acidic
solution, and then, metal oxides such as RuO2, Co3O4, and
MnO2 were electroplated on the inner surface of the nano-
porous Au framework. The metal oxide shell signicantly
enhanced the electrochemical performance of the core–shell
hybrid materials. In particular, the RuO2–NPG cathode showed
a higher capacity and better electrocatalytic activity compared
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Fig. 7(a) High-angle annular dark field – scanning TEM (HAADF-STEM) image and EDS mapping of C, O, and Ru elements in the CNT@RuO2
composite. (b) HAADF-STEM and (c) bright field (BF)-STEM images, and (d) schematic illustration of the CNT@RuO2 structure. (e) Discharge–
charge profiles of CNT and CNT@RuO2 cathodes measured at a current density of 385 mA gcarbon 1. (f) Plot of the capacity vs. cycle number for
the CNT@RuO2 composite cathode at a current density of 500 mA gtotal 1. Reprinted with permission from ref. 121.

with Co3O4–NPG and MnO2–NPG (Fig. 9(c)). The low over-
potential originates from the unique nanostructure composed
of highly conductive nanoporous Au decorated with a thin
metal oxide layer, in which there are abundant open spaces
indicating that Li2O2 accumulation as well as a large number of
active reaction sites could be secured.
Bimetallic alloys may have superior catalytic activity
compared with monometallic materials due to the combination
of ligand, geometric, and ensemble effects.145,158,159 Luo et al.145
studied 1D porous AgPd–Pd nanotubes (NTs) synthesized by
a galvanic replacement reaction for use in LABs (Fig. 9(d) and
(e)). Compared with the pure Ag nanowires, the Pd-alloyed Ag
NTs showed an improvement in round-trip efficiency of 78%
as well as a high discharge capacity of 2650 mA h g 1 at
0.2 mA cm 2. According to the cyclic voltammograms and
rotating disk electrode results in an O2-saturated non-aqueous
electrolyte, the porous NT structure showed favourable rechar-
geability and excellent round-trip efficiency, owing to rapid O2
and electrolyte diffusion through the NTs as well as the
continuous conductive network. These nanostructured noble
metals, however, are scarce, expensive, high-weight, and diffi-
cult to handle for mass production and scaling up.
Transition metal carbides have been the object of consider-
able interest, because they exhibit superior electrical conduc-
tivities and excellent surface physicochemical properties
resulting from the similarity of their d-orbital states to those of
noble metals.160 As an alternative cathode, commercially avail-
able TiC nanoparticles have been proposed for LAB applica-
tions. Thotiyl et al.132 demonstrated a TiC-based cathode with
a DMSO electrolyte, which showed a greatly reduced over-
potential compared with the carbon cathode. The TiC
cathode retained more than 98% of its initial capacity

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Fig. 8 (a) Schematic design of FeO-passivated porous carbon deco-
rated with Pd nanoparticles by using the ALD process. TEM micro-
graphs of (b) pristine, (c) FeO-deposited, and (d) Pd/FeO-deposited
3DOm porous carbon. Reprinted with permission from ref. 109.
(350 mA h gTiC 1) aer 100 cycles, which is mainly attributable
to the reduced side reactions associated with electrode and
electrolyte degradation. The XPS analysis suggested that the
excellent stability of the TiC cathode was attributable to the
Fig. 9 (a) BF-TEM and (b) HRTEM images of RuO2-NPG with a core–shell structure. (c) Discharge–charge profiles of porous Au cathodes with
different metal oxide shells measured at a current density of 100 mA gAu 1 with a limited capacity of 300 mA h gAu 1. Reprinted with permission
from ref. 144. (d) Schematic diagram of the formation of AgPd nanotubes via the galvanic replacement reaction process and corresponding (e–h)
HRTEM images. Reprinted with permission from ref. 145.
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combination of its high electrical conductivity and the presence
of some oxidized TiOC phase on the surface that was resistant
against nucleophilic attack. There are still some arguments,
however, about the reproducibility of the TiC cathode's perfor-
mance; thus, further studies are needed to prove the suitability
of TiC as a cathode for LABs.13 Recently, Kundu et al.150 reported
surface-passivated Mo2C nanobers with low charging poten-
tials (3.2 V vs. Li/Li+) as a carbon-free cathode. On discharging,
conductive passivation layers of LixMoO3 were formed via the
chemical reaction of Li2O2 and native MoO2 on the carbide. On
charging, Li2O2 was then oxidized at low potentials simulta-
neously with LixMoO3 due to their similar redox potentials.
Nevertheless, the competitive oxidation reactions of Li2O2 and
LixMoO3 take place at the expense of the cathode, which
degrades the long-term cyclability of LABs. This implies that the
structural properties of oxide-passivating layers formed on the
carbide surface strongly affect the stability of the carbide.
A wide range of metal oxides also have been investigated as
carbon-free cathodes for LABs. A conductive indium-tin-oxide
(ITO) supported Ru nanoparticle (Ru/ITO) cathode was intro-
duced as a carbon-free cathode for LABs by Zhou's group.129 ITO
is known to be stable, while Ru has been proven to act as an
efficient bi-functional catalyst for the ORR and OER. The
Ru/ITO cathode exhibited a much lower charging overpotential
and better cycling stability for up to 50 cycles in comparison to
carbon-only and Ru/carbon cathodes. The superior catalytic
activity of Ru and the absence of carbon in the Ru/ITO cathode
could lead to impressive electrochemical performance of the
corresponding LABs. Since the achievable specic capacity of
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the Ru/ITO cathode was low due to the high mass of ITO, they
suggested a carbon-free cathode (Ru/STO) comprising Ru
nanocatalyst particles supported on lightweight Sb-doped tin
oxide (STO).135 The Ru/STO cathode exhibited a relatively large
specic capacity of 750 mA h g 1 compared with Ru/ITO as well
as high round-trip efficiency. More recently, highly conductive
metal oxides such as Ti4O7 with the Magnéli phase and hollow
RuO2 have been proposed as carbon-free cathodes. A carbon-
free cathode composed of Ti4O7 with crystallite sizes of
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10–20 nm was developed by Kundu et al (Fig. 10(a)).146 The
highly porous nano-Ti4O7 cathode showed reversible ORR and
OER activity in LABs with very low onset potential for charging
(3.0–3.5 V vs. Li/Li+). The majority of the charge process (85%)
occurred below 4.0 V vs. Li/Li+. Consistent with the results for
the TiC cathode, it was demonstrated that the TiO2 x interphase
on the surface of Ti4O7 facilitates electron ow from the elec-
trochemical reaction sites and inhibits corrosion of the
cathode. Li et al.147 reported highly conductive hollow RuO2
having a single-crystal conductivity of 104 S cm 1, which is
much higher than that for carbon and even some metals
(Fig. 10(b) and (c)). RuO2 has been demonstrated to exhibit high
catalytic activities towards the ORR and OER, and its unique
hollow structure has a large number of electrochemically active
sites in the hollow cores, i.e., two- and/or three-phase bound-
aries among the O2, electrolyte, and cathode. The hollow RuO2
Fig. 10 (a) Schematic illustration of the effective oxidation of Li2O2 on
a highly conductive Magnéli Ti4O7 cathode. Reprinted with permission
from ref. 146. (b) SEM and (c) TEM images of RuO2 hollow spheres. (d)
Discharge-charge profiles and (e) cycling performance of the RuO2
hollow sphere cathode at a current density of 500 mA g 1 over 100
cycles. Reprinted with permission from ref. 147.
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prepared by a template method showed excellent electro-
chemical performance and rate-capability. A high reversible
capacity of 1400 mA h g 1 with low overpotentials (0.13 V for
discharging and 0.54 V for charging) could be attained when
this cathode was fully discharged/charged for 100 cycles in
a DMSO-based electrolyte (Fig. 10(d) and (e)). The superior
electrochemical performance of the hollow RuO2 cathode was
attributed to the good conductivity, large surface area, and high
catalytic activity of the hierarchically porous, metallic RuO2
towards both the ORR and the OER.
4.2.2.2 Free-standing-type electrode design. Considering the
fact that polymeric binders are also prone to degradation in the
presence of Li2O2 in LABs,48,161,162 a more versatile approach to
carbon-free cathode design is to fabricate “free-standing”
cathodes. It is expected that the free-standing 3D porous
structures without any carbon or binder will enable stable and
reversible operation of the LAB. Metals and alloys, which
possess high electrical conductivity and catalytic activities, have
been directly grown on porous conducting metal (Ni)
substrates. Liao et al.152 reported a free-standing nanoporous Ru
electrode formed on Ni foam via a simple galvanic replacement
method (Fig. 11(a)–(c)). The LAB with the porous Ru/Ni exhibi-
ted good cycle stability over 100 cycles at a high current density
of 200 mA gRu 1 with a low overpotential of 0.5 V. The superior
performance can be attributed to: (i) high catalytic activity and
high surface area of Ru (58.3 m2 gRu 1); (ii) intimate contact
between Ru and Ni; and (iii) porous architecture enabling the
facile permeation of O2.
Kim et al.153 proposed a free-standing Ni nanowire decorated
with Au nanoparticles (Fig. 11(d)–(f)). To obtain the porous and
free-standing conducting electrode, Ni nanowire arrays were
synthesised by an electroplating method using an aluminium
oxide template (pore size 20 nm), and then, Au nanoparticles
(size <30 nm) were directly deposited on the Ni nanowire. The
Au/Ni electrode showed a high capacity of 590 mA h gAu 1 at
a high current density of 500 mA gAu 1 and a stable cycling
performance over 100 cycles. Luo et al.154 fabricated the Pt–Gd
alloy lm on porous Ni foam by using a pulsed laser deposition
method (Fig. 11(g)–(i)) and demonstrated its feasibility as
a cathode for LABs. They proposed that the outstanding cata-
lytic properties of the Pt–Gd lm electrode result mainly from
the closely packed spacing of the polycrystalline catalyst coating
on the substrate as well as the synergistic activity of Pt and Gd.
Metal oxides can be deposited directly on current collectors by
various synthesis techniques, including electrodeposi-
tion,130,131,136,137 and hydrothermal138–140,148,149 and chemical vapour
deposition (CVD).151 Co3O4-based materials, which possess high
electrocatalytic activities toward the ORR and OER, have been
extensively investigated as non-carbon materials for free-standing
cathodes.127,130,131,136,139–141,148,149 For the rst time, Cui et al.127 re-
ported a free-standing-type (carbon- and binder-free) Co3O4
cathode directly grown on conductive Ni foam by using a simple
chemical deposition reaction. The cathode exhibited a higher
specic capacity with better round-trip efficiency than the
conventional carbon cathode. A similar concept of free-standing
(carbon- and binder-free) cathode design for LABs was proposed
by Riaz et al.,130 achieved by growing Co3O4 on a Ni foam current
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Fig. 11 (a and b) SEM images of the nanoporous Ru electrode formed on the Ni foam (Ru/Ni). (c) Discharge–charge profiles of the Ru/Ni cathode
at a current density of 200 mA gRu 1 with a limited capacity of 1000 mA h gRu 1. Reprinted with permission from ref. 152. (d) SEM and (e) TEM
images of Ni nanowire decorated with Au nanoparticles (Au/Ni). (f) Discharge-charge profiles of the Au/Ni cathode at a current density of
500 mA gAu 1. Reprinted with permission from ref. 153. (g) FESEM and (h) HRTEM images of the Pt–Gd thin film deposited on porous Ni foam
(Pt–Gd/Ni). (i) Discharge–charge profiles of the Pt–Gd/Ni cathode at a current density of 0.1 mA cm 2 for 100 cycles. Reprinted with permission
from ref. 154.

collector. A two-step process involving electrodeposition and
chemical conversion was employed to fabricate nanowires,
nanosheets, and nanoowers on macroporous Ni foam. These
free-standing Co3O4-based cathodes displayed less overpotential
by 520 mV during charging as compared to a free-standing CNT-
based cathode. The reduced overpotential for the free-standing
Co3O4 cathode is due to the stable and inert nature of Co3O4 in the
presence of Li2O2 and the reduced carbonate formation, as
conrmed by XPS and SEM analyses. Zhao et al.131 also synthe-
sized hierarchical porous Co3O4 lms in the form of free-standing
hollow akes on Ni foam by using an electroplating method.
Mesopores with different sizes can be obtained in the akes by
adjusting the calcination temperature. The porous lms calcined
at 300  C offered a high capacity of 2460 mA h g 1 and a stable
cycling performance. In order to further improve the catalytic
activity, recently, free-standing Co3O4 cathodes decorated with
noble metal catalysts such as Pt and Pd have been sug-
gested,141,148,149 and Leng et al. showed remarkably improved
electrochemical performance compared with the undecorated
Co3O4 cathode (Fig. 12(a)–(c)).
Free-standing cathodes have been fabricated using manganese
or titanium oxides as well, which provide the advantages of envi-
ronmental friendliness, low cost, high elemental abundance, and
easy preparation. Recently, Hu et al.137 reported a free-standing
3-MnO2 cathode with a sponge-like nanostructure, which was
directly grown on Ni foam through a facile electrodeposition. The
free-standing 3-MnO2 cathode showed a high capacity of
6300 mA h g 1 at 500 mA g 1 and enhanced cyclability (>120
cycles) without controlling the capacity cut-off. The superior
performance is attributed to the unique 3D nanoporous structure
and abundant structural defects in 3-MnO2. Zhao et al.142 proposed
a free-standing cathode made of TiO2 nanotubes and Pt

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Journal of Materials Chemistry A Review

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Fig. 12 (a) SEM and (b) TEM images of Pd-decorated Co3O4 nanowires (Pd/Co3O4), with the insets showing higher magnification. (c) Discharge–
charge profiles of the Pd/Co3O4 cathode at a current density of 10 mA cm 2 with a limited capacity of 300 mA h g 1. Reprinted with permission
from ref. 149. (d) SEM and (e) HRTEM images of TiO2 nanotubes decorated with Pt nanoparticles (Pt/TNT), marked by red circles in (e). (f)
Discharge–charge profiles of the Pt/TNT cathode at a current density of 1 A gPt 1 with a limited capacity of 1000 mA h gPt 1. Reprinted with
permission from ref. 142. TEM images of (g) NiCo2O4 (NCO) nanoneedles and (h) nanoneedles decorated with MnO2 nanoflakes (MnO2/NCO). (i)
Discharge–charge profiles of the MnO2/NCO cathode at a current density of 100 mA g 1 for 250 cycles. Reprinted with permission from ref. 138.

nanoparticles (Fig. 12(d)–(f)). The TiO2 nanotube arrays were grown
directly on Ti foam using anodic oxidation, and Pt nanoparticles
were decorated on the anodized Ti foam using cool sputtering.
Beneting from the stability of TiO2, the LAB could be cycled
reversibly for 140 cycles at high current densities of 1 or 5 A g 1.
In addition to making the cathode chemically and electro-
chemically stable by introducing carbon-free designs, tailoring
structures on the nanoscale is of vital importance for high-
performance LABs. Riaz et al.138 reported a nanostructured
cathode based on NiCo2O4 nanoneedle arrays decorated with
MnO2 nanoakes (Fig. 12(g)–(i)). Ternary NiCo2O4 with higher
electrical conductivity than binary Co3O4 was grown in the form
of nanoneedles on the skeleton of the Ni foam current collector
by a hydrothermal method, and then, MnO2 nanoakes were
hydrothermally deposited on the NiCo2O4 nanoneedle arrays.
The LAB with the NiCo2O4@MnO2 cathode showed a high
discharge capacity of 2372 mA h g 1 and excellent cycling
stability. The chemical and morphological studies proved the
reversible formation and decomposition of Li2O2 on the cathode
surface. Moreover, the excellent electrochemical performance can
be traced back to the properly tailored nanoarchitecture: namely,
the large amount of pores among the 1D nanoneedles that were
available for Li2O2 storage and for mass transport, and the large
number of active reaction sites on the nanoakes.
5. Concluding remarks and
perspectives
According to the growing demand for efficient energy storage
systems,163,164 LAB technology has been highlighted as

14064 | J. Mater. Chem. A, 2016, 4, 14050–14068 This journal is © The Royal Society of Chemistry 2016

Review
a promising candidate in the eld of energy storage. Even
though there are many advantages of LABs over other candi-
dates, their poor cycling performance and low round-trip effi-
ciency associated with high charging potential have been
pointed out as inevitable problems for practical use. Thus, one
of the most important concerns is to improve the stability and
reversibility of the cathode to reduce the charging potential and
thereby improve the cycling performance and round-trip effi-
ciency of LABs. As we summarized above, there are two main
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streams in the research on cathodes for LABs: (i) nano-
structured porous carbon cathodes and (ii) carbon-free cath-
odes, both of which are being extensively investigated. Recently,
thanks to nanotechnology, the structural diversity of carbon
materials has been contributing to the advancement of nano-
structured porous carbon cathodes. In practice, various struc-
tural modications of carbon materials and robust cathode
design have lead to strong enhancement of the battery perfor-
mance of LABs. As supposed, the physicochemical properties of
the cathode (i.e. porosity, pore size, surface area, and electrical
conductivity) have shown strong relationships to the electro-
chemical performance of LABs. Nevertheless, further improve-
ment of LABs is limited by side reactions induced by carbon
instability in non-aqueous electrolytes. Numerous attempts
have been made to secure cathodes with long-term stability, but
the carbon instability remains a pending problem at this
moment.
Because of this, more recently, carbon-free cathodes have
been proposed as alternatives for LABs. Various noble metals or
metal oxides have been explored, based on a better fundamental
understanding of the reaction mechanisms. Note that the
reversibility of LABs can be signicantly improved by mitigating
side reactions arising from the carbon instability. Unfortu-
nately, the achievable battery performance of LABs employing
carbon-free cathodes cannot meet the requirements for
commercial use yet. It is necessary, therefore, to develop
advanced cathodes that are able to facilitate reversible electro-
chemical reactions between Li and O2. On the other hand, we
emphasize that the direction of further research will be based
on our understanding of the fundamental reaction mecha-
nisms. Some parts of the reaction mechanism in the LABs have
not been fully understood. More attention should be paid to
clarifying the reaction mechanism based on Li–O2 electro-
chemistry. This would be helpful for providing practical
guidelines for the development of high-performance cathodes
for LAB applications.
Acknowledgements
This work was supported by the R&D Programs of the Korea
Institute of Energy Research (Project No. KIER B6-2515) and
National Research Council of Science & Technology (Project No.
CAP-14-2-KITECH).
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