Lithium-air batteries: Challenges coexist

with opportunities
Cite as: APL Mater. 7, 040701 (2019); https://doi.org/10.1063/1.5091444
Submitted: 01 February 2019 . Accepted: 28 March 2019 . Published Online: 30 April 2019

Chengyi Wang, Zhaojun Xie, and Zhen Zhou

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APL Mater. 7, 040701 (2019); https://doi.org/10.1063/1.5091444 7, 040701

© 2019 Author(s).
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

Lithium-air batteries: Challenges coexist

with opportunities
Cite as: APL Mater. 7, 040701 (2019); doi: 10.1063/1.5091444
Submitted: 1 February 2019 • Accepted: 28 March 2019 •
Published Online: 30 April 2019

Chengyi Wang,1 Zhaojun Xie,1,a) and Zhen Zhou1,2,a)

AFFILIATIONS
1
School of Materials Science and Engineering, Institute of New Energy Material Chemistry, Nankai University,
Tianjin 300350, China
2
School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, China

a)
Authors to whom correspondence should be addressed: zjxie@nankai.edu.cn and zhouzhen@nankai.edu.cn

ABSTRACT
Lithium-air batteries have caught worldwide attention due to their extremely high theoretical energy density and are regarded as powerful
competitors to replace traditional lithium ion batteries. However, it is rather critical how to maximize the capacity while keeping good cycling
stability, which has impeded practical applications of Li-air batteries for decades. Although admirable achievements have been made in recent
years, there are still many unsolved issues for developing practical Li-air batteries. In this review, the challenges are pointed out and the
recent progress in cathodes, anodes, and electrolytes is also summarized for Li-air batteries, as well as the relationship between each part for
better electrochemical performances. Furthermore, some inspiring results on constructing advanced Li-air batteries are discussed particularly.
Finally, opportunities and perspectives are also provided.
© 2019 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license
(http://creativecommons.org/licenses/by/4.0/). https://doi.org/10.1063/1.5091444

I. INTRODUCTION
Modern human society is undergoing rapid economic and
social development and causes enormous pressure on power sup-
plement.1–3 There have been three industrial revolutions in the his-
tory of mankind, and each could be regarded as a revolution in the
mode of production along with the change of energy supply meth-
ods. Today, billions of tons of fossil fuels are consumed every year
to maintain the high-speed development, resulting in serious envi-
ronmental pollution and global warming issues.4,5 It is urgent to
develop and utilize renewable energy sources and eliminate high pol-
lution industries.6 Thanks to the efforts of worldwide researchers,
remarkable progress has been made in seeking and utilizing renew-
able energy sources, such as wind energy, solar energy, geother-
mal energy, and tidal power.7 Unfortunately, these newly developed
technologies cannot serve as stable energy sources alone because of
their natural sensibility toward weather, landform, or other environ-
mental conditions. Energy storage and conversion devices must be
used together to break these limitations. Lithium-ion batteries (LIBs)
are one of the most widely used energy storage techniques which can
convert electric energy to chemical energy reversibly. However, tra-
ditional LIBs cannot meet the requirements for the daily increased
demand due to their low theoretical capacity (387 Wh kg−1 ).8,9
Developing new energy storage and conversion systems with higher
energy density and efficiency has become a worldwide challenge.
In the past decade, rechargeable lithium-air batteries have aroused
worldwide attention due to their ultrahigh theoretical energy density
(3500 Wh kg−1 ) and become one of the most competitive candidates
to replace LIBs (Fig. 1).10–14 The earliest study of Li–O2 batteries
can date back to 1987 when Semkow and Sammells developed a
stabilized ZrO2 solid electrolyte and operated their Li–O2 batteries
at 650–800 ○ C.15 In 1996, Abraham and Jiang constructed the first
prototype of room temperature Li–O2 batteries with a polymer elec-
trolyte.16 Since the attempt at the earlier stage, researchers all around
the world have contributed more to explore the potential of Li-air
batteries, and significant advancements have been achieved. Up to
now, many different types of Li-air batteries have been developed
and they can be divided into four types based on the electrolyte used:
nonaqueous (aprotic organic solvents and ionic liquids), aqueous,
hybrid, and solid-state batteries.17–19 Among the four types, most
studies were based on nonaqueous types because of their compar-
atively high energy density accompanied with simple battery struc-
tures. Hence, in this review, we will only focus on the recent progress
of nonaqueous Li–O2 batteries.

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© Author(s) 2019
 APL Materials
FIG. 1. Theoretical energy densities of different rechargeable batteries (data from
Refs. 4 and 21).
The structure of nonaqueous Li–O2 batteries is similar to that
of Li-ion half-cells; both consist of Li metal anodes, separators, elec-
trolytes, and cathodes, except that the cathodes of Li–O2 batteries are
exposed to atmosphere/oxygen. Yet the mechanism of Li–O2 batter-
ies is different from traditional LIBs based on the Li intercalation
mechanism. Li–O2 batteries are half-open systems which use oxy-
gen from ambient air as recourses to store and convert energy. In
the discharging process, lithium metal is oxidized to Li+ and then
migrates to the air cathode. In the meantime, oxygen accepts elec-
trons from the external circuit and combines with Li+ to form dis-
charge products on the air cathode. When charging the batteries,
the electrochemical processes are reversed. Typically, the main dis-
charge product of Li–O2 batteries is Li2 O2 , and the electrochemical
reactions are shown below18,20,21
Anode : 2Li ↔ 2Li+ + 2e− ,
Cathode : 2Li+ + O2 + 2e− ↔ Li2 O2 ,
Total : 2Li + O2 ↔ Li2 O2 (Eocv = 2.96 V vs Li/Li+ ).
However, the exploration of Li–O2 batteries is still at its early
stage. There are some critical barriers for the practical application
of Li–O2 batteries, such as low energy efficiency, short cycle life,
and poor rate capability. These drawbacks are mainly caused by
the sluggish oxygen reduction reaction (ORR) and oxygen evolution
reaction (OER) kinetics and slow mass transport on the cathode.18
Hence, many researchers devoted themselves to find new cathodes
with both ORR and OER activity to facilitate the kinetics. As for the
slow mass transport, special architectures with sufficient pore struc-
tures are necessary. The achievement in preparing efficient cathodes
with unique porous nanostructures will be summarized and emphat-
ically discussed. Although cathodes play a very important role in the
whole system, it is hard to say that cathodes are the only handicap
of Li–O2 batteries. Anodes, electrolytes, and other related parts can
also affect the performance of batteries which will also be introduced
in this review. Moreover, the influence of CO2 , H2 O, and N2 in
ambient air should also be seriously treated to move Li–O2 batteries
APL Mater. 7, 040701 (2019); doi: 10.1063/1.5091444
© Author(s) 2019
RESEARCH UPDATE scitation.org/journal/apm
forward to Li-air batteries. We believe that practical Li-air batteries
with excellent electrochemical performances can be achieved only
when every unit plays its roles and successfully works together as a
whole system.
II. CATHODES
Obviously, the cathode plays a crucial role as the primary
site for electrochemical reactions. Due to the half-open system and
complicated reaction mechanism of Li–O2 batteries, many unique
requirements must be considered when designing cathode materi-
als. We summarize as three critical rules: high catalytic activity, high
electronic conductivity, and high porosity. First, the cathode mate-
rials must have high bifunctional catalytic activity to facilitate slug-
gish ORR/OER processes and thus can reduce the overpotential of
Li–O2 batteries. Second, high electronic conductivity is required to
provide fast electron supplement for fast electrochemical reactions.
Third, high porosity is indispensable because the discharge prod-
ucts are generated and stored in the cathode. Besides, high porosity
can also sustain fast mass transport and sufficient electrolyte infiltra-
tion. Basically, cathode materials can be divided into three groups:
carbon-based materials, precious metal-based materials, and non-
precious metal-based materials. We will select some typical reports
on each kind of cathode materials and introduce them in this section.
A. Carbon-based materials
Carbon-based materials have always been a hot topic due to
many attractive advantages including light weight, low cost, high
conductivity, large specific surface area, and tunable pore struc-
ture. Thus, carbon-based materials have widely been investigated
and applied for many energy storage devices, such as LIBs, sodium-
ion batteries, and supercapacitors.3,22 Additionally, carbon-based
materials can achieve remarkable bifunctional ORR/OER catalytic
activity by heteroatom doping which makes them one of the most
promising cathode materials for Li–O2 batteries. In this part, we
will only focus on carbon-based materials. Compositing carbon with
metal-based materials will be discussed elsewhere.
1. Activated carbon
Activated carbon is widely used as a conductive additive in bat-
teries and has already been commercially available. Regardless of
the advantages of low cost and high electrical conductivity, acti-
vated carbon also processes extremely large specific surface area
(up to 2000 m2 /g)23 which is one of the most important factors
as cathodes for Li–O2 batteries. Until now, various activated car-
bon samples including Ketjenblack (KB), Super P, XC-72, BP2000,
Calgon, Denda black, and JMC have been used as cathode materi-
als for Li–O2 batteries.18,24–27 Tran et al. evaluated the relationship
between pore-size distribution and discharge capacity of a series of
activated carbon and found that carbon materials along with high
surface areas and large pores were more favorable for Li–O2 bat-
teries.28 The surface property of carbon materials is another factor
which can influence the performance of Li–O2 batteries. It was sug-
gested that the discharge voltage decreases with increasing graphi-
tization because of the lack of defects which serve as active sites for
ORR.29 However, the porosity and graphitization are only intrinsic
factors that determine the electrochemical performance. Extrinsic
7, 040701-2
 APL Materials
factors also play their important parts. Zhang and co-workers inves-
tigated the influence of carbon loading on the performance of Li-air
batteries and maximized the area-specific capacity of KB-based air
cathodes with a carbon loading of 15.1 mg cm−2 .26 They suggested
that the uniformity of pore sizes was crucial, and larger mesopore
volumes would lead to higher capacity.
2. Advanced carbon materials
As mentioned above, the cathode materials of Li–O2 batteries
require a large specific surface area and suitable porosity. Reduc-
ing the dimension of materials is one of the promising strategies
to significantly enlarge the specific surface area and construct var-
ious porous structures. Preparing low-dimensional carbon materi-
als has widely been applied including one-dimensional (1D) forms
[carbon nanotubes (CNTs) and carbon nanofibers (CNFs)] and
two-dimensional (2D) forms (graphene). These advanced carbon
materials have proved admirable activity for Li–O2 batteries due to
their unique structures.30–32 For example, an extremely high specific
capacity of 34 600 mAh g−1 was obtained at a current density of
500 mA g−1 with free-standing multiwalled carbon nanotube
(MWCNT) papers as cathodes for Li–O2 batteries.33 Interestingly,
the growth direction of CNTs can be controlled via special syn-
thetic methods and surprisingly ordered structures can be achieved
[Figs. 2(a) and 2(b)].34 This binder-free well-aligned CNT fibrils
with hierarchical pores can efficiently promote the electrochemical
reactivity, provide continuous access of oxygen and Li+ , and min-
imize the undesirable clogging by uniformly distributing the dis-
charge products. A similar strategy has also been used to prepare
ordered CNT arrays.35
Graphene has shown extraordinary performances in many
fields, especially as electrocatalysts and energy storage materials due
to their amazing unique structure and properties. The high electrical
conductivity and specific surface area (theoretically 2630 m2 g−1 )36
of graphene can meet the demands as cathodes for Li–O2 batter-
ies very well. For instance, Yoo et al. found that the discharge
catalytic activity of carbon-based materials can be even compa-
rable to 20 wt. % Pt/C catalysts when using chemical exfoliated
graphene nanosheets (GNSs) as cathode materials for Li-air bat-
teries.32 According to their experimental results, heat treatment
can improve the cycling stability of GNSs due to two reasons:
first, the decreased sp3 /sp2 ratio and, second, the removal of func-
tional groups from the GNS surface. However, the ideal 2D lay-
ered structure of graphene cannot take the full advantage due to
the low content of highly active edge atoms. Xiao and co-workers
APL Mater. 7, 040701 (2019); doi: 10.1063/1.5091444
© Author(s) 2019
RESEARCH UPDATE scitation.org/journal/apm
demonstrated three-dimensional (3D) graphene frameworks with
unique bimodal porous structure as air cathodes for Li–O2 bat-
teries and achieved an exceptionally high discharge capacity up to
15 000 mAh g−1 .37 Two reasons were responsible for the excellent
performance. One was the special porosity which contains numer-
ous large tunnels facilitating continuous supplement of oxygen while
nanoscale pores connected with each other providing tri-phase
regions for ORR/OER. Besides, the authors found that Li2 O2 parti-
cles prefer to form on the defects and functional groups on graphene
through density functional theory (DFT) computations. The influ-
ence of functional groups was further experimentally investigated
by oxidizing reduced graphene oxide (rGO) with different process-
ing times (from 30 min to 3 days).38 The highest capacity of 59 792
mAh/gcarbon was obtained by using the rGO sample oxidized for
3 day as the cathode.
Although significant improvements have been made by intro-
ducing various kinds of advanced carbon materials, the overpoten-
tial was still too large and far from satisfaction due to the intrin-
sic limited catalytic activity of pristine carbon materials. Hence,
researchers turn to develop new approaches to get better catalytic
activity. Among the approaches, heteroatom doping has proved an
attractive strategy to improve the ORR/OER activity. For exam-
ple, Li et al. prepared nitrogen-doped carbon nanotubes with up
to 10.2 at. % incorporated nitrogen as cathode materials for Li–O2
batteries and achieved improved capacity compared with commer-
cial CNTs.30 In 2014, Zhang et al. prepared a hierarchical carbon-
nitrogen architecture with both macrochannels and mesopores
through a sol-gel route for Li–O2 batteries and achieved a long cycle
ability of 161 cycles39 [Figs. 3(a)–3(e)]. In addition to the advantage
of forming hierarchical architectures, pyridinic N in N-rich carbon
materials can also provide excellent oxygen adsorption according
to first-principles computations. Computations disclosed that in-
plane pyridinic N had higher activity in facilitating the nucleation of
Li2 O2 clusters compared with pristine and graphitic N.40 By doping
one or more kinds of heteroatoms into different carbon substrates,
many bifunctional cathode materials have been applied to Li–O2
batteries, such as N-doped CNTs,41 N-doped graphene,42–46 S-doped
graphene,47,48 and N,S co-doped graphene.49 Generally speaking, N
doping is a powerful way to improve the catalytic activity of carbon
materials by manipulating the local electronic structures and pro-
viding more active sites. Sulfur-doped graphene was found to have a
better cycling stability compared with N-doped graphene due to the
better stability of –C–S–C– and –C==S– structures than the –C–N–
structure.48
FIG. 2. SEM images of CNT fibrils at (a) low magnification
(inset: large area image of the air electrode) and (b) high
magnification.
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 APL Materials
FIG. 3. (a) The discharge profiles of the HMCN cathode at 50 and 100 mA/g. (b) The limited depth of discharge at 600 mAh/g at a current of 200 mA/g with the HMCN
cathode. (c) The corresponding plot of discharge and charge capacity against the cycle number and (d) full discharge/charge curves between 2.0 and 4.3 V at 100 mA/g. (e)
Schematic illustration of hierarchical carbon-nitrogen material with both macrochannels and mesopores as cathodes for Li–O2 batteries.
3. Other carbon materials with special structures
With the growing study of Li–O2 batteries, the primary require-
ments for the structure of cathode materials have been gradually
established. Hierarchical mesoporous/macroporous structures can
effectively improve the performance of Li–O2 batteries. So far, based
on the fast development of nanotechnology, many special struc-
tured carbon materials have been designed and prepared for Li–
O2 batteries.50–54 Guo et al. used silica as the template and pre-
pared 3D ordered mesoporous/microporous carbon sphere arrays
(MMCSAs) for Li–O2 batteries and achieved larger capacity than
commercial graphene oxide (GO) or CNTs [Figs. 4(a)–4(g)].50 The
Dai group designed a vertically aligned nitrogen-doped coral-like
carbon nanofiber (VA-NCCF) array as the cathode for Li–O2 bat-
teries.51 Benefiting from its unique vertically aligned structure and
N-doping induced catalytic activity, the overpotential was reduced
to only 0.3 V with an energy efficiency up to 90%. Their Li–O2 bat-
teries also presented an ultralong cycling stability for more than 150
cycles with the capacity cutoff of 1000 mAh g−1 .
B. Precious metal-based materials
Precious metals are important catalysts for ORR and OER
applications. Thus, it was easy to come up with the idea of serv-
ing as cathode materials for Li–O2 batteries. Up until now, many
studies have proved the superiority of precious metals and their
oxides including Au,55,56 Pt,57–59 Pd,60–62 Ru,63–68 and Ir.69–72 Peng
et al. used nanoporous gold (NPG) as cathodes and dimethyl sul-
foxide (DMSO) as electrolytes and found that the kinetics of the
charge process was about 10 times faster than that of carbon elec-
trodes.55 In addition, precious metal-based cathodes can reduce the
overpotential of Li–O2 batteries not only with their high catalytic
activity but also by changing the morphology and crystal struc-
ture of discharge products. Different from large particles of Li2 O2
in CNT cathodes, the Byon group found that poorly crystalline
APL Mater. 7, 040701 (2019); doi: 10.1063/1.5091444
© Author(s) 2019
RESEARCH UPDATE scitation.org/journal/apm
Li2 O2 films uniformly deposited on the surface with RuO2 /CNT
as the cathode.63 This special morphology can enlarge the contact
area between Li2 O2 and CNTs and significantly reduce the overpo-
tential during the charge process. Aiming to improve the catalytic
activity of Pd-based catalysts, Jun and co-workers used the com-
binatorial high-throughput optical screening method and investi-
gated the catalytic activity of a series of binary Pd-based catalysts.60
According to their experimental results, the Pd–Ir alloy with the
composition of 88:12 presented the highest ORR activity for hybrid
Li-air batteries, with ∼30% higher energy efficiency than that of
Pd/C cathodes.
C. Nonprecious metal-based materials
Although admirable achievements have been made by using
noble metal-based cathodes to reduce the overpotential of Li–O2
batteries, the high cost of precious metals was an unavoidable draw-
back that dramatically limited their practical applications. To replace
expensive noble metals, many researchers chose to use cheap transi-
tion metal-based materials as cathodes for Li–O2 batteries. In this
section, we will discuss the recent progress in transition metal-
based cathode materials including metals, oxides, carbides, nitrides,
sulfides, and their composites.
1. Transition metals
Highly dispersed transition metal nanoparticles possess excel-
lent catalytic activity toward ORR or OER and are regarded as
promising substitution for precious metals. Flexible free-standing
Co nanoparticles anchored CNT grafted multichannel carbon fibers
(Co@NS/CNT-MCFs) were prepared through an electrospinning
method and directly used as the cathode for Li–O2 batteries.73 The
authors attributed the excellent electrochemical performances to
the special interconnected structure incorporated with abundant Co
nanoparticles and N and S codoping which can provide a large
number of active sites. Chen and co-workers prepared Co and Cu
7, 040701-4
 APL Materials
FIG. 4. Characteristics of the as-prepared MMCSAs: [(a) and (b)] SEM images and
[(c)–(f)] TEM images with different magnifications. (g) Discharge curves of Li–O2
batteries at 50 mA g−1 with different weight percentages of MMCSAs in porous
catalytic electrodes: (a) 0, (b) 5, (c) 10, (d) 30, (e) 50, and (f) 80 wt. %.
bimetallic nanoparticles deposited on graphene (CoCu/graphene) as
bifunctional cathodes for Li–O2 batteries.74 Benefiting from the syn-
ergistic effect of Co and Cu, their batteries presented a superior rate
capability of 7955 mAh g−1 at 800 mA g−1 with long-term cycling
APL Mater. 7, 040701 (2019); doi: 10.1063/1.5091444
© Author(s) 2019
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stability as long as 122 cycles (200 mA g−1 with a cutoff capac-
ity of 1000 mAh g−1 ). The Kanga group presented Co-embedded
bamboolike N-doped CNT bundles (Co-b-NCNTs) as cathodes for
Li–O2 batteries.75 Their Li–O2 batteries exhibited excellent elec-
trochemical performance with a high initial discharge capacity of
28 968 mAh g−1 (200 mA g−1 ) and long cycling stability for more
than 200 cycles.
2. Transition metal oxides
Among transition metal oxides, Co oxide catalysts attracted the
most attention due to their low cost, varied compositions, and even
comparable catalytic activity toward noble metals. In 2015, the Liu
group prepared vacancy-bearing CoO (CoO–A) and vacancy-free
CoO (CoO–N) by calcinating different cobalt salts and found that
the synergetic effect of CoO and oxygen vacancies can significantly
reduce the overpotential and achieve much better cycling stability.76
Platelike Li2 O2 was found after the first discharge [Figs. 5(a)–5(f)].
The authors demonstrated that oxygen vacancies can facilitate the
electronic conductivity and Li+ migration as well as serve as active
sites for O2 and Li2 O2 . Note that creating oxygen vacancies is a
very common method to improve the performances of transition
metal oxides. In the work by Wang et al., the electrocatalytic activ-
ity of Co3 O4 can be boosted by tuning the inner oxygen vacancies
and the exterior Co3+ /Co2+ ratios.77 The superiority of creating oxy-
gen vacancies in other transition metal oxides was also confirmed.
For example, Zhang et al. evaluated the influence of the concen-
tration of oxygen vacancies in MoO3 nanosheets by controlling
the reduction time.78 According to their experimental results, high-
concentration oxygen vacancies were more favorable for better per-
formances. Mu and co-workers used the rapid laser-scan method to
prepare oxygen-deficient NiO as cathode materials for Li–O2 bat-
teries. Oxygen adsorption was another important parameter that
can directly influence the electrochemical performances of cath-
ode materials. The effect of oxygen adsorption on the formation of
Li2 O2 was studied with Co3 O4 -based cathode materials by the Chen
group.79 They demonstrated that the solution growth of toroid Li2 O2
was dominated in cathodes with weak oxygen adsorption, while the
strong oxygen adsorption drove the surface growth model to thin
films. Apart from the oxygen adsorption, Li+ adsorption and LiO2
adsorption are also critical to the final battery performance. The
Yan group successfully adjusted the adsorption of different tran-
sition metal oxides to fabricate α-MnO2 and Co3 O4 composites
which can achieve embedded growth of large Li2 O2 aggregations.80
In their work, experimental results and first-principles computations
showed that α-MnO2 nanorods prefer to form uniform Li2 O2 parti-
cles due to the preferential Li+ adsorption and similar LiO2 adsorp-
tion energies of different crystal faces. However, the LiO2 adsorption
energies of various Co3 O4 crystal faces were quite different, asso-
ciated with their preferential O2 adsorption, and Li2 O2 nanosheets
were the main discharge product. Thus, the authors combined these
two oxides and used α-MnO2 nanorods to provide initial nucle-
ation sites for Li2 O2 deposition while Co3 O4 nanosheets continu-
ously to provide dissolved LiO2 for deeper discharge. As mentioned
above, different crystal faces may exhibit different performances,
but the inherent relationship has not been clearly demonstrated.
To investigate the effect of different crystal faces, the Lu group
prepared a series of Cr2 O3 with varying fractions of high-energy
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 APL Materials
faces via a TiO2 inhibitor.81 They demonstrated that increasing
the fraction to the high-energy facet can increase the OER activity
[Figs. 6(a)–6(e)].
Binary transition metal oxides can sometimes bring better cat-
alytic activity than a single one.82 So far, a large series of binary
transition metal oxides have been prepared for Li–O2 batteries,
such as NiCo2 O4 ,83 NiFe2 O4 ,84,85 MnCo2 O4 ,86,87 MnMoO4 ,88 and
CoMoO4 .89 He and co-workers evaluated a series of Cux Co3−x O4
nanorods with different Cu2+ concentrations.90 The catalytic activity
can be enhanced by replacing more Co2+ with Cu2+ and dispersing
more Cu2+ in the catalyst surface. The authors believed that suitable
charge transfer from Li2 O2 to the catalyst was a critical parameter
for better electrochemical performance.
3. Transition metal carbides, sulfides, and nitrides
Although inspiring progress has been made in transition
metal oxides, their intrinsically poor electronic conductivity was an
inevitable problem that limited the performance of Li–O2 batter-
ies. Hence, some researchers turned their eyes to transition metal
carbides which have a relatively higher electronic conductivity than
transition metal oxides. Among all those transition metal carbides,
Mo2 C has become one of the most attractive materials due to its
multiple valence states, high electrochemical activity, and relatively
affordable cost.91,92 In the work by Zhu et al., a composite of carbon-
wrapped Mo2 C nanoparticles and carbon nanotubes directly on
Ni foam was prepared as the cathode material for Li–O2 batteries
and significantly improved the electrochemical performance with a
ultralong cycling life up to 300 cycles.93 Hou and co-workers sys-
tematically studied the catalytic activity of Mo2 C/CNT and found
that Mo2 C can stabilize the intermediate species by forming amor-
phous (Li–O–O)x –Mo2 C discharge products which dramatically
reduced the charge overpotential.94 Another Mo based material-
molybdenum disulfide (MoS2 ) also showed high catalytic activity
as cathode materials for Li–O2 batteries. For example, Asadi and
co-workers prepared MoS2 nanoflakes combined with an ionic liq-
uid as a cocatalyst for Li–O2 batteries. The round-trip efficiency of
their batteries was as high as 85%.95 Interestingly, Wang et al. pre-
sented a hybrid Li-ion and Li–O2 battery which also used MoS2
as the cathode material. In their hybrid system, both Li-ion and
APL Mater. 7, 040701 (2019); doi: 10.1063/1.5091444
© Author(s) 2019
RESEARCH UPDATE scitation.org/journal/apm
FIG. 5. SEM images of CoO–A and
CoO–N based cathodes for Li–O2 bat-
teries at different states. [(a)–(c)] The
cathode catalyzed by CoO–A: (a) before
discharge; (b) after the first discharge;
and (c) after the 8th charge. [(d)–(f)] The
cathode catalyzed by CoO–N: (d) before
discharge; (e) after the first discharge;
and (f) after the 8th charge.
O anions were reversibly stored by forming a Li2 MoO2 S2 com-
pound which is isostructural to Li2 MoO4 . Strikingly, the voltage
gap of this hybrid electrochemistry was as low as 20 mV with a
high energy efficiency of 99%.96 Brushlike Co4 N nanorods anchored
on carbon nanofiber (Co4 N/CNF) membranes were designed to
achieve an ultrastable (177 cycles) Li–O2 battery with high reversibil-
ity [Figs. 7(a)–7(g)].97 The authors demonstrated that a thin oxide
layer on the surface of Co4 N could promote the formation of film-
like Li2 O2 , thus resulting in a smaller overpotential of only 1.23 V at
700 mAh g−1 .
The catalytic activity of cathode materials is one of the most
important parameters which directly determines the electrochemi-
cal performance of Li–O2 batteries. Carbon-based materials, espe-
cially heteroatom-doped carbon-based materials, have high elec-
trical conductivity, tunable porosity, and low cost. However, the
catalytic activity and cycling stability are not good enough. On
the contrary, metal-based materials usually show admirable cat-
alytic activity. However, precious metals are rather expensive, metal
oxides have low electronic conductivity, and metals and their com-
pounds are apt to aggregate. Therefore, composites of metal-based
and carbon materials could bring many unique superiorities includ-
ing but not limited to improve the electronic conductivity, provide
high active sites, disperse nanoparticles, and enlarge the specific
area.
III. ANODES
Higher energy density and longer cycling stability are eternal
targets for energy storage devices. Based on the special electrochem-
istry of Li–O2 batteries, the active material, oxygen, can be regarded
as infinity from air, so the capacity mainly depends on how much
lithium can be provided by anodes. Lithium metal anodes have the
highest theoretical capacity of 3860 mAh g−1 and the lowest electro-
chemical potential of −3.04 V vs standard hydrogen electrode (SHE),
which can maximize the energy density of Li–O2 batteries.98 How-
ever, lithium metal anodes have many challenges to be solved before
their practical application. First, lithium metal anodes for Li–O2 bat-
teries also face the same problems as in traditional lithium batteries,
such as Li dendrite growth, unstable solid-electrolyte-interface (SEI)
7, 040701-6
 APL Materials RESEARCH UPDATE scitation.org/journal/apm

FIG. 6. Materials with high fraction of high-energy facets as a superior OER catalyst. (a) Galvanostatic charge profiles of Li–O2 cells employing commercial Cr2 O3 , 0TiCrOx -
400, 0.5TiCrOx -400, and 1TiCrOx -400 as catalysts in comparison with Ru/Vulcan carbon. [(b)–(d)] Average charge voltage as a function of fraction of high-energy facets (b).
Voltage and gas evolution profiles during charging using (c) 1TiCrOx -400 and (d) commercial Ru/Vulcan carbon as the cathode. (e) Schematic illustration of (012) inhibition
in Cr2 O3 crystals by introducing anatase TiO2 with a low lattice mismatch.

films, and infinite relative volume change. Second, lithium metal
anodes for Li–O2 batteries have to face special challenges due to the
unique electrochemical reactions and half-open configuration. The
reactions between lithium and oxygen species from the cathode side
dramatically reduce the Coulombic efficiency and cycling stability
of Li anodes. Fortunately, with the growing understanding of Li–O2
batteries, the importance of Li anodes was gradually clarified. Cre-
ating protecting films on Li metal anodes was the most widely used
strategy. This strategy can be divided into two kinds: SEI films and
artificial films. For the first one, the most commonly used method
was adding electrolyte additives to form a stable SEI film. For exam-
ple, LiNO3 was believed to be a good choice to form a stable SEI layer
and proved also useful in Li–O2 batteries.99,100 For the second strat-
egy, putting an extra membrane on the Li metal anode is a popular
way. In the work by Park and co-workers, a layer of polyvinylidene
fluoride-hexafluoropropylene (PVdF-HFP) and Al2 O3 was used to

APL Mater. 7, 040701 (2019); doi: 10.1063/1.5091444 7, 040701-7

© Author(s) 2019
 APL Materials
FIG. 7. (a) Schematic images of the Co4 N/CNF fabrication procedure. SEM images and photograph images (insets) of (b) CNF, [(c) and (d)] Co(OH)F/CNF, and [(e)–(g)]
Co4 N/CNF with different magnifications.
suppress the decomposition of electrolytes on the surface of Li metal
anodes.101 By adding this protecting layer, more than 3 times higher
cycling life was achieved compared with the cell with bare Li as the
anode. Interestingly, Zhang et al. introduced an extremely simple
and efficient method to grow a protective polymer film on Li anodes
by dipping Li anodes into 1,4-dioxacyclohexane (DOA).102 Another
possible way to solve the stability issue of anodes was to replace the
Li metal anode with other lithium containing materials. The Zhou
group found a new way to suppress the attack of oxygen species
by using a durable SEI film to protect Si anodes.103 Their Li–O2
APL Mater. 7, 040701 (2019); doi: 10.1063/1.5091444
© Author(s) 2019
RESEARCH UPDATE scitation.org/journal/apm
batteries with Si anodes exhibited significantly improved cycling
stability along with low overpotentials.
IV. ELECTROLYTES
Searching for suitable electrolytes for Li–O2 batteries was a
long and tortuous story. The first aprotic Li–O2 battery proposed
by Abraham and Jiang adopted a mixture of ethylene carbonate
(EC) and propylene carbonate (PC) as solvents and LiPF6 as the Li
salt.16 Unfortunately, carbonate-based electrolytes were found to be
7, 040701-8
 APL Materials
unstable for Li–O2 batteries.104,105 Li2 CO3 was detected as a side
product causing a higher charge overpotential when PC-based elec-
trolytes were used. Therefore, researchers turned to sulfoxide-based
electrolytes with many advantages such as low volatility, low viscos-
ity, high O2 diffusion, and especially superoxide tolerability.106 How-
ever, some researchers argued that DMSO-based electrolytes can be
decomposed during the charge process.107,108 Thanks to the excel-
lent stability toward superoxide species and good solubility for Li+
and oxygen, ether-based electrolytes stood out from various organic
electrolytes and have been the most widely used electrolyte for Li–O2
batteries. In addition, the stable operation voltage window could be
as high as 4.5 V which is very important to achieve Li–O2 batteries
with long cycling life.18,109
Apart from the stability issue, the evaporation of organic sol-
vents is an unavoidable problem. Quasisolid-state and especially
solid-state electrolytes may be a better choice to solve this issue.
Besides, using quasisolid-state or solid-state electrolytes can dramat-
ically suppress the crossover of superoxide and peroxide species,
which in turn protects Li metal anodes. Another advantage is that the
safety level of the batteries could be better because of the absence of
flammable organic solvents. Many related reviews have already sum-
marized the progress in developing quasisolid-state and solid-state
electrolytes.18,110–112 Here, we would not introduce the details.
So far, we have introduced many kinds of solid catalysts for
Li–O2 batteries. But the catalytic ability of these solid catalysts is
limited by the poor connection between catalysts and discharge
products. This limitation is even worse when approaching the end
of discharge/charge processes. In other words, some of the dis-
charge products cannot be catalyzed because they are too far from
the catalysts. There is another important kind of electrocatalysts
named redox mediators (RMs) which can facilitate the forma-
tion/decomposition of all discharge products because they are dis-
solved in the electrolyte and can react with all the discharge prod-
ucts. Redox mediators can be divided into two types according to
the processes that are catalyzed: ORR RMs and OER RMs. Taking
the OER RMs as an example, the reaction processes can be described
as follows: first, during the charge process, RMs give electrons to
the cathode and are oxidized to a higher oxidation. Then, the oxi-
dized RMs diffuse to the discharge products and oxidize them to Li+
and O2 and return to their initial low oxidation states [Figs. 8(a) and
8(b)]. The catalytic behavior for ORR RMs is similar to that of OER
RMs except that it is a reduction process. Up to now, many RMs
APL Mater. 7, 040701 (2019); doi: 10.1063/1.5091444
© Author(s) 2019
RESEARCH UPDATE scitation.org/journal/apm
have been explored for Li–O2 batteries and some inspiring results
were reported. The first report of OER RM was presented by the
Bruce group in 2013.113 They used tetrathiafulvalene (TTF) as an RM
and successfully reduced the charge potential below 3.5 V with 100
cycles. Since then, various kinds of inorganic and organic RMs were
discovered such as 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO),114
LiI,115 and tris[4-(diethylamino)phenyl]amine (TDPA)116 for OER
and 2,5-di-tert-butyl-1,4-benzoquinone (DBBQ)117 and phenol118
for ORR. The Kang group selected a series of organic RM candidates
and studied the catalytic activity along with the stability in Li–O2
batteries. They demonstrated that the level of ionization energies
was the critical parameter to select suitable RMs for Li–O2 batter-
ies.119 However, the biggest problem of RMs for Li–O2 batteries is
the shuttle reactions, which means that RMs may crossover the sep-
arator and react with Li metal anodes. More attention should be paid
to put RMs into practical application.
V. FROM Li–O2 BATTERIES TO Li-AIR BATTERIES
Most reported results are based on pure oxygen. To make a
practical Li-air battery, the effects of CO2 , moisture, and N2 in ambi-
ent air are critical for the battery performances. Although the con-
centration of CO2 in ambient air is very low, the impact of CO2
cannot be ignored because of its larger solubility in organic sol-
vents.120 Besides, Li2 CO3 is chemically more stable than Li2 O2 , caus-
ing a larger charge overpotential and more serious decomposition
issues of electrolytes. Thus, some researchers aimed to find a suitable
catalyst to facilitate the decomposition of Li2 CO3 for better cycling
stability. The Zhang group prepared iridium-decorated boron car-
bide (Ir/B4 C) as the cathode material which can decompose Li2 CO3
below 4.37 V.121 However, the influence of CO2 was not all bad. In
2011, Takechi and co-workers investigated a series of different ratios
of O2 and CO2 mixed gas for Li–O2 /CO2 batteries.122 The capacity
of mixed gas batteries could reach nearly twice larger than that of Li–
O2 batteries. Inspired by the progress in studying the effect of CO2 , a
newly developed energy storage system named rechargeable Li–CO2
batteries came into researchers’ sight which used CO2 as the working
gas.123–125 In one word, the influence of CO2 on the battery perfor-
mances is an intricate handicap due to the lower kinetics of CO2
compared with that of O2 . More efforts should be paid to develop
new electrocatalysts with higher catalytic activity. The effect of H2 O
on Li–O2 battery performances is a complicated issue. On the one
FIG. 8. Role of RM for Li–O2 batter-
ies. (a) Schematic illustration of the reac-
tion mechanism of RM for Li–O2 batter-
ies. During the charge, RM (blue circles)
is oxidized near the electrode surface
(step 1, electrochemical reaction), and
then RM+ (red circles) chemically oxi-
dizes Li2 O2 to 2 Li+ (green circle) and
O2 gas (orange circles). Finally, RM+ is
reduced to the initial state of RM (step
2, chemical reaction). (b) Schematic dis-
charge (black line) and charge profiles
of Li–O2 batteries with (blue line) and
without RM (red line).
7, 040701-9
 APL Materials
hand, some researchers demonstrated a higher charge overpoten-
tial when H2 O was involved in the electrolyte.126,127 On the other
hand, some people believed that additional H2 O is an efficient sol-
uble additive which can dramatically reduce the overpotential and
enlarge the discharge capacity.128–130 Nitrogen as the major con-
stituent of ambient air was also found to be electrochemically active
toward lithium.131,132 All in all, the development of Li-air batteries is
still at the primary stage. There is a long way to achieve a practical
Li-air battery which can be operated in ambient air.
VI. CONSTRUCTING ADVANCED SYSTEMS
Up to now, we have introduced many strategies to achieve bet-
ter electrochemical performances by optimizing the specific part of
Li–O2 batteries including cathodes, anodes, and electrolytes. Here,
we would talk about some recent development that breaks the tradi-
tional rules of Li–O2 batteries. In the work by Asadi and co-workers,
an extremely long cycling life of up to 700 cycles was reported
in a simulated air atmosphere.133 The authors used several meth-
ods to achieve this amazing stability including a Li2 CO3 /C coated
anode, a MoS2 cathode, and a mixed electrolyte. According to their
experiments, the protected lithium anode together with an ionic liq-
uid/DMSO mixed electrolyte can greatly reduce the influence of CO2
and H2 O which was the primary request for a practical Li-air battery.
Their work reminded everyone of the importance of thinking in a big
picture and proved that combining suitable protected anodes, mod-
ified electrolytes, and highly catalytically active cathodes together
as a system can achieve high-performance Li-air batteries. Inter-
estingly, the Nazar group reported a special Li–O2 system based
on a reversible four-electron conversion with ultralow overpoten-
tial (<0.2 V at 0.1 mA cm−2 ) and superior cycling stability.134 To
tune the reaction pathway from Li2 O2 to Li2 O, the working temper-
ature was set at 150 ○ C. Thus, the batteries used in this work were
quite different from traditional nonaqueous Li–O2 batteries. The
electrolyte used in this work was LiNO3 /KNO3 eutectic molten salts
which can work at high temperatures. The cathode was a noncar-
bonaceous Ni/Lix NiO2 composite to catalyze the reversible forma-
tion and decomposition of Li2 O. The authors ascribed their success
to several reasons. First, lithium oxide was less chemically reactive
than lithium peroxide which can suppress side reactions. Second,
molten salt electrolytes and noncarbonaceous cathodes were more
chemically stable compared with organic electrolytes and carbon-
based cathodes. These two reports proved that every part of the bat-
tery was crucial to the final electrochemical performance. A practical
Li-air battery with high performances could be achieved when the
problems of cathodes, anodes, and electrolytes were totally solved.
VII. CONCLUSION AND PERSPECTIVE
In summary, we have reviewed the recent progress and chal-
lenges of developing high-performance Li-air batteries. Li-air bat-
teries are undergoing high-speed development and admirable break-
through in improving their electrochemical performance which has
been made in the past years. The extremely high theoretical energy
density of Li-air batteries encourages people to put efforts into their
practical applications. However, the gap between idea and reality still
remains huge, and we cannot deny the fact that the exploration of
Li-air batteries is still in their early stage.
APL Mater. 7, 040701 (2019); doi: 10.1063/1.5091444
© Author(s) 2019
RESEARCH UPDATE scitation.org/journal/apm
Li-air batteries are complicated systems including anodes, cath-
odes, electrolytes, and separators, and each part is critical to deter-
mine the overall electrochemical performance. The essential chal-
lenge is how to improve the cycling stability of every single part
under such complicated superoxide/peroxide containing situations
while keeping a good energy efficiency and rate capability. For cath-
ode materials, it requires high bifunctional catalytic activity, high
electronic conductivity, and high porosity. The high catalytic activity
can be achieved by compositing metal-based and carbon materials.
For anodes, the tolerability toward O2 , CO2 , and H2 O should be high
enough to guarantee the stability for cycling the batteries in ambient
air. To maximize the energy density of Li-air batteries, constructing
protective layers on the surface of lithium metal anodes would be
a desired method. In addition, the safety issues, such as the growth
of lithium dendrites and the flammable organic electrolyte, should
also be considered. Considering the special half-open structure of
Li-air batteries, quasisolid or even solid-state electrolytes may be the
best choice once the problem of low ionic conductivity is solved. It
can be expected that an ultimate practical Li-air battery with long
cycling life, high energy density, and efficiency will be achieved in
the future.
ACKNOWLEDGMENTS
This work was supported by Tianjin Municipal Science and
Technology Bureau (No. 17JCQNJC06400) in China.
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