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Lithium-Air Battery: Promise and Challenges

G. Girishkumar,* B. McCloskey, A. C. Luntz, S. Swanson, and W. Wilcke
IBM Research - Almaden, 650 Harry Road, San Jos
e, California 95120

ABSTRACT The lithium-air system captured worldwide attention in 2009 as a

possible battery for electric vehicle propulsion applications. If successfully developed,
this battery could provide an energy source for electric vehicles rivaling that of gasoline
in terms of usable energy density. However, there are numerous scientific and technical
challenges that must be overcome if this alluring promise is to turn into reality. The
fundamental battery chemistry during discharge is thought to be the electrochemical
oxidation of lithium metal at the anode and reduction of oxygen from air at the cathode.
With aprotic electrolytes, as used in Li-ion batteries, there is some evidence that the
process can be reversed by applying an external potential, i.e., that such a battery can be
electrically recharged. This paper summarizes the authors' view of the promise and
challenges facing development of practical Li-air batteries and the current under-
standing of its chemistry. However, it must be appreciated that this perspective
represents only a snapshot in a very rapidly evolving picture.

M
ankind's total power consumption is currently 14 TW
and is projected to roughly triple by 2050.1 At present,
oil represents 34% of the world's total primary energy
source. It accounts for 40% of the total CO2 emission and is a
major cause of geopolitical instability.1 Since the majority of oil is
used for automobile and light truck applications, a transition to
an electrified road transportation system should be a societal
goal of utmost importance.2 This is already beginning with the
advent of hybrid electric vehicles (EVs), and will accelerate as
plug-in hybrid vehicles and ultimately pure EVs are developed.
The major technical hurdle for the complete electrification of
road transportation is the insufficient storage capacity of current
batteries, severely limiting the range of practical EVs. The Li-air
battery was initially proposed in the 1970s for automotive appli-
cations.3 In the last year, that interest in Li-air has grown
sharply, resulting in over 14 research articles published in the
first quarter of 2010 alone. The Li-air battery potentially has
much higher gravimetric energy storage density compared to all
other battery chemistries, and this has led to strong interest
in whether such batteries could be developed for powering
EVs, enabling driving ranges comparable to gasoline powered
automobiles.4
The Battery 500 Project by IBM and its partners, as well as
many other research groups have initiated research programs
on Li-air batteries to evaluate their potential as batteries for
automotive propulsion applications. The “500” stands for a
target range of 500 miles/800 km per charge, which translates
into a battery capacity of about 125 kWh at an average use of
250 Wh/mile for a standard family car. Li-air batteries may also
play important roles in other areas, such as powering laptops
and remote sensors or for robotic uses. However, the require-
ments of automotive applications shape the thrust of most
research programs. At this stage, research focuses principally on
determining the basic scientific principles underlying the opera-
tion of Li-O2 batteries (rather than Li-air). Section II discusses
system level requirements for a successful EV application
battery. Section III describes various architectural (chemical)
approaches for Li-air batteries and compares key trade-offs.
Section IV describes current experimental and theoretical
studies of the aprotic Li-O2 battery, with emphasis on the air
cathode. Section V discusses the anode, while section VI dis-
cusses the status and challenges of using air rather than O2 as
the reactant. Section VII summarizes the research we believe
needs to be performed to develop practical Li-air batteries.
System Level Requirements for Automotive Propulsion and
the Li-Air Battery. The key criteria for practical EV propulsion
batteries are energy density, cost, lifetime (measured in years
and miles), and safety.
The key criteria for practical EV
propulsion batteries are energy
density, cost, lifetime (measured in
years and miles), and safety.
Gravimetric and Volumetric Energy Density: The energy
density of gasoline is 13 000 Wh/kg, which is shown as its
theoretical energy density in Figure 1. The average tank-to-
wheel efficiency of the U.S. fleet is 12.6%; therefore the usable
energy density of gasoline for automotive applications is
approximately 1700 Wh/kg.1 This is shown as the “practical”
Received Date: April 27, 2010
Accepted Date: June 24, 2010
Published on Web Date: July 02, 2010

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Figure 1. The gravimetric energy densities (Wh/kg) for various
types of rechargeable batteries compared to gasoline. The theore-
tical density is based strictly on thermodynamics and is shown as
the blue bars while the practical achievable density is indicated by
the orange bars and numerical values. For Li-air, the practical
value is just an estimate. For gasoline, the practical value includes
the average tank-to-wheel efficiency of cars.
energy density for gasoline in Figure 1. Since the efficiency of
electric propulsion systems (battery-to-wheels) are about 90%,
a 10-fold improvement of the current energy densities of Li-ion
batteries, which are typically between 100 and 200 Wh/kg (cell
level), would bring electric propulsion systems on-par with
gasoline, at least as measured by gravimetric energy density.
However, there is no expectation that current batteries such as
Li-ion will ever come close to the target of 1700 Wh/kg. New
chemistries are required to achieve this goal.
The oxidation of 1 kg of lithium metal releases 11 680 Wh/kg,
not much lower than that of gasoline. This is shown as the theo-
retical energy density of a Li-air battery in Figure 1. However,
practical energy densities for Li-air batteries will be far less.
Existing metal-air batteries, such as Zn/air, typically have a practi-
cal energy density of about 40-50% of their theoretical density.
However, one can safely assume that even fully developed Li-air
cells will never achieve such an excellent ratio, because lithium is
very light, and therefore the overhead of the battery structure,
electrolytes, and so forth will have a much larger impact.
Fortunately, an energy density of 1700 Wh/kg for the fully
charged battery corresponds only to 14.5% of the theoretical
energy content of lithium metal. It is not inconceivable that
such an energy density, at the cell level, may be achievable,
given intensive and long-term development work. The energy
density of the complete battery system may be only half of the
density realized at the cell level.
The volumetric energy density (measured in Wh/L) of the
battery is also an important design consideration. This re-
quirement is best captured by allocating a maximum volume
of 300 L (family car) for the battery and its auxiliary systems. A
driving range of 500 miles (800 km) requires 125 kWh
capacity (at 250 Wh/mile), thus a 300 L volume limit dictates
that the specific gravity of the battery, including the space
allocated for air channels inside the battery and the air-
handling system, must not be less than 0.5 kg/L. Note that
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the specific air flow (kg air per kW of power generated) into a
Li-air battery, assuming the exhaust air from the battery had
an oxygen content of 17%, is comparable to the specific
airflow of internal combustion engines.
Power Density and Cost: While Li-air systems offer the
promise of very high energy densities, their power density
(measured in W per kg of battery mass) is currently very low.
During discharge, oxygen is thought to be reduced in the
presence of lithium ions to form lithium oxides, and during
charge the chemical reaction reverses to evolve oxygen gas.
Both reactions occur at the surfaces of the cathode. Thus
very large internal surface areas, both in a microscopic and a
macroscopic sense, are required. Prototype aprotic Li-air cells
deliver current densities in the order of 1 mA/cm2. It will be
critical to increase this current density by at least 1 order of
magnitude. Even then, the macroscopic surface area to supply
the total power for a propulsion battery is very large. For
example, a battery with 100 kW power output at a cell voltage
of 2.5 V and a current density of 25 mA/cm2 will require a total
internal surface area of 160 m2, equal to the internal surface of
the human lung.
One way to reduce the power density requirements is to
create an electric hybrid propulsion system where a small capa-
city but high power battery, for example, based on Li-ion
technology, provides power for short periods of high demand,
such as during acceleration. This is possible since the ratio of
average-to-peak power demand in a car is only about 1:10.
Electrical Energy Efficiency: Current Li-air cells exhibit
large overvoltages, i.e., the charging voltage is considerably
higher than the discharge voltage. This corresponds to a
low cycle electrical energy efficiency, currently on the order
of 60-70%. Practical propulsion batteries should exhibit
“round-trip” energy efficiencies of 90%. The detailed me-
chanisms underlying these high over voltages are currently
not understood, but hopefully can be substantially reduced by
the choice of catalysts.
Liftetime and Cyclability: Current Li-air cells have been
demonstrated with up to about 50 cycles with only moderate
loss in capacity.5 Therefore, future research efforts need to
focus on improving the capacity retention during cycling.
Nevertheless, the total number of charge cycles of large
propulsion batteries would not necessarily need to be high
given the large energy capacity of Li-air cells. For example, a
battery designed for a lifetime of 150 000 miles and support-
ing a 500 mile range will need to be recharged only 300 times
(full cycle equivalent). But many tons of air will have to pass
through a battery during its lifetime, and even minute accu-
mulations of moisture (for aprotic batteries) or products of
side reactions will be detrimental.
Safety: The batteries of EVs will be held initially to extre-
mely high safety standards, much higher than gasoline cars.
Typical thermal runaway of a Li-ion battery due to overcharg-
ing or internal shorts is not a possibility in Li-air batteries
because of the rate-limited surface nature of the reaction, i.e.,
the reactant O2 is not stored in the battery. However, there are
two other safety concerns to be considered. First, the desired,
though not mandatory, use of lithium metal anodes is a
well-known safety problem, since lithium metal tends to form
dendrites, which can short-circuit the battery and react
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aggressively with many contaminants. Second, the presumed
dominant reaction product of aprotic cells is Li2O2, which
is a strong oxidizer. Combined with an organic electrolyte,
this could lead to safety issues in an accident. However,
preliminary experiments at IBM indicate that no thermal
exothermic reactions between Li2O2 and common electro-
lytes occur at temperatures below the melting point of lithium
metal (180 °C). This safety concern does not exist in aqueous
cells.
In conclusion, the requirements for large capacity auto-
motive propulsion batteries are extensive, but quite well-
defined. They will serve as guidelines for the research to be
carried out on Li-air systems. At present, automotive propul-
sion batteries are just beginning the transition from nickel
metal hydride to Li-ion batteries, after nearly 35 years of
research and development on the latter. The transition to
Li-air batteries (if successful) should be viewed in terms of a
similar development cycle.
Automotive propulsion batteries
are just beginning the transition
from nickel metal hydride to Li-ion
batteries, after nearly 35 years of
research and development on the
latter. The transition to Li-air bat-
teries (if successful) should be
viewed in terms of a similar devel-
opment cycle.
Architectures of Li-Air Batteries. Currently, four chemical
architectures are being pursued worldwide, which are outlined
in Figure 2. These include three versions with liquid electrolytes:
a fully aprotic liquid electrolyte, an aqueous electrolyte, and a
mixed system with an aqueous electrolyte immersing the
cathode and an aprotic electrolyte immersing the anode. The
fourth approach is an all-solid-state battery with a solid electro-
lyte. The fundamental electrochemistry depends upon the
electrolyte around the cathode.
In an aprotic electrolyte, the fundamental cathode dis-
charge reactions are thought to be
2Li þ O2 f Li2 O2
and possibly
2Li þ ð1=2ÞO2 f Li2 O
In an aqueous cathode electrolyte, the fundamental reac-
tions are
2Li þ ð1=2ÞO2 þ 2Hþ f 2Liþ þ H2 O ðacidic mediaÞ
2Li þ ð1=2ÞO2 þ H2 O f 2LiOH ðalkaline mediaÞ
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The battery chemistry for the all-solid-state battery is not
clear at this point in time, but is presumably the same as
that for the aprotic electrolyte. The aprotic version was first
6
investigated by Abraham and Jiang and further developed
7 5,8,9
principally by Read et al. and Bruce et al. The fully
aqueous version is being developed by Polyplus,10 while the
mixed electrolyte configuration is also being developed by
Polyplus10 and Wang and Zhou.11 A fully solid-state Li-air
battery was recently reported by Kumar et al.12 Each config-
uration has specific advantages and presents definite scien-
tific and engineering challenges, so that the ultimate choice
for the best configuration is still an open question. A brief
preview of some of these issues is given below. While Figure 2
and much of the discussion here assumes lithium metal as
the anode, alloy anodes are also an option for Li-air batteries
and are discussed briefly in section V.
In the aprotic liquid version (see Figure 2), the lithium
anode is in contact with the electrolyte and forms a stable
solid electrolyte interface (SEI). At the air-breathing cathode
(currently porous carbon cathodes similar to polymer electro-
lyte membrane (PEM) fuel cell cathodes), insoluble Li2O2 (and
perhaps Li2O) is thought to be formed via the oxygen reduc-
tion reaction (ORR). There is some evidence that, with
catalysts present, Li2O2 will undergo the oxygen evolution
reaction (OER) at sufficiently high applied recharge voltages5
so that the aprotic configuration could be the basis for an
electrically rechargeable Li-air battery. This will be discussed
in detail later in this article. Both for the aqueous electrolyte
configuration and the mixed electrolyte configuration, the
cathode chemistry is identical, and there is no evidence at this
time that the electrochemical reaction is reversible, except by
mechanically removing the reaction products and replacing
them with fresh reactants. The great advantage of the aqueous
or mixed electrolyte configuration is that the discharge reac-
tion product is soluble in H2O, eliminating the cathode clogg-
ing, volume expansion, and electrical conductivity issues
of the aprotic architecture.13 A difficult challenge for aque-
ous and mixed systems is the development of good Li-ion con-
ducting membranes, which protect the anode from reacting
vigorously with H2O (see section V). For the aqueous system,
this requires the development of a lithium metal and water-
stable artificial SEIs (see Figures 2 and 3). In the mixed
electrolyte system, an aprotic electrolyte is in direct contact
with the lithium metal anode so that a natural SEI is formed
on the lithium metal. This minimizes the difficult require-
ment that the membrane protecting the lithium metal from
H2O is also stable against reduction by lithium metal. Visco
et al. have demonstrated an aprotic Li-air battery with an
artificial ceramic SEI to protect the anode.10 This cell could be
cycled over 60 times at 0.4 mA/cm2 in air with 50% relative
humidity. The protection of lithium metal from contamination
is discussed in section V. All four configurations will ultimately
have to solve the difficult problem of developing a high
throughput air-breathing system that passes O2 and keeps out
environmental contaminants (e.g., H2O, CO2, N2). Because
only the aprotic configuration of a Li-air battery has shown
any promise of electrical rechargeability, this configuration
has attracted the most effort worldwide to date, and we focus
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Figure 2. Four different architectures of Li-air batteries, which all assume the use of lithium metal as the anode. The three liquid electrolyte
architectures are aprotic, aqueous, and a mixed aprotic-aqueous system. In addition, a fully solid state architecture is also given. Principal
components are as labeled in the figure. Spontaneously occurring SEIs on the lithium anode are given as dashed lines, while artificial SEIs
are given as solid lines.

principally on this configuration for the remainder of this

perspective.

All four configurations will ulti-

mately have to solve the difficult
problem of developing a high
throughput air-breathing system
that passes O2 and keeps out
environmental contaminants.

Aprotic Li-Air Battery. A typical design for aprotic Li-air

batteries is shown in Figures 2 and 4. It is composed of a
metallic lithium anode, an electrolyte comprising a dissolved
lithium salt in an aprotic solvent, and a porous O2-breathing
cathode composed of large surface area carbon particles
and catalyst particles, both bound to a metal mesh using a
binder.
The chemistry proposed for the aprotic Li-air battery is as
Figure 3. Schematic drawing of the lithium metal-electrolyte inter-
follows.6 During the discharge of the cell, an oxidation reaction face choices. Both the complicated natural SEI formed by reduction
occurs at the anode (Li f Liþ þ e-). The electrons flow through of the electrolyte and an artificial SEI, e.g., Li-ion-conducting ceramic,
an external circuit and the lithium ions generated from this are shown as examples. Adapted from refs 14 and 15.
reaction reduce oxygen to form Li2O2 (and possibly Li2O) in the
cathode. The standard potential for the discharge reaction U0 is (U > U0), the reaction above is thought to be reversed, i.e.,
given by the thermodynamics of the reaction as U0 = 2.96 V, lithium metal is plated out on the anode, and O2 is evolved (i.e.,
using the Nernst equation. At externally applied potentials generated) at the cathode (Figure 4).The simplest net reaction

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Figure 4. Schematic operation proposed for the rechargeable
aprotic Li-air battery. During discharge, the spontaneous electro-
chemical reaction 2Li þ O2 f Li2O2 generates a voltage of 2.96 Vat
equilibrium (but practically somewhat less due to overpotentials).
During charge, an applied voltage larger than 2.96 V (∼4 V is
required due to overpotentials) drives the reverse electrochemical
reaction Li2O2 f 2Li þ O2.
envisioned for the aprotic battery is a two-electron process:
2Li þ O2 f Li2 O2 ðdischargeÞ ð1Þ
Li2 O2 f 2Li þ O2 ðchargeÞ ð2Þ
The lithium anode is in contact with the electrolyte and forms
a stable SEI, which protects the metal from further reaction with
the electrolyte. This is quite similar to the formation and proper-
ties of an SEI at carbon-lithium anodes in conventional Li-ion
batteries.16 Examples of aprotic electrolytes used to date include
organic carbonates (ethylene carbonate, propylene carbonate,
dimethyl carbonate), ethers (tetrahydrofuran (THF), dioxolane),
and esters (γ-butyrolactone), which solvate lithium salts, such as
LiPF6, LiAsF6, LiN(SO2CF3)2, and LiSO3CF3 and have high oxida-
tive stabilities.17
A typical discharge-charge cycle of a Li-O2 cell is shown in
Figure 5, and is quite similar to others in the literature.5 The cell
consisted of a lithium metal foil as the anode, a 250 μm thick
glass mat fiber separator, and a porous cathode constructed
from high surface area Super P (Super P is a conductive carbon
black and is a product of TIMCAL Graphite & Carbon) carbon
particles mixed with R-MnO2 nanorods serving as a catalyst,
both uniformly distributed and bound to a 1.6 mm-thick
metallic nickel foam current collector with PVDF binder.
The composition of the active cathode materials by weight
percent were carbon:R-MnO2:PVDF = 54:10:36. The separator
and cathode were flooded with 1 M LiN(SO2CF3)2 [LiTFSI] in
propylene carbonate, which served as the electrolyte. The cell
construction was a spring loaded Swagelok design with active
electrode areas of 1.2 cm2. The initial open circuit voltage (OCV)
of this cell is ∼3.3 V, which is significantly higher than U0. This
high OCV likely reflects a mixed potential effect due to inter-
calation of Li-ions into the R-MnO2 particles. This process
terminates quickly as the cell is discharged because there is
not much R-MnO2 present. Without the catalyst in the cathode,
the OCV is ∼3.1 V, still slightly higher than U0 by 0.15 V. The
working voltage of this cell during discharge is approximately
2.6-2.7 V, which is significantly less than U0. This difference is
called the discharge overpotential ηdis. The discharge capacity of
this Li-O2 cell is also much lower than its theoretical capacity
given by the void volume of the cathode, ∼1%. This is most
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Figure 5. A single measured discharge-charge cycle for an aprotic
Li-O2 cell (based on SP carbon) operated at ∼0.1 mA/cm2 current
density. This gives the cell output voltage for discharge or the nece-
ssary applied potential for charge at the given current density as a
function of the charge per gram of carbon in the cathode (mAh g-1).
Details of this cell are given in the text. Discharge and charge
directions are given by the labeled arrows in the figure. The thermo-
dynamic potential is given by the dashed line, and the overpotentials
for discharge ηdis and charge ηchg are indicated by the arrows.
likely due to the insolubility of discharge products in the
nonaqueous organic electrolyte, which causes a buildup of
discharge products on the cathode surface, inhibiting the flow
of reactants (O2, Liþ, and electrons) to the active surface.
During constant-current charging of the cell, the voltage
increases to approximately 4.0 V (Figure 5). Hence the charge
overpotential (ηchg) is significantly greater than the discharge
overpotential (ηdis). Thus, at present, the electrical energy effi-
ciency for a discharge-charge cycle is only 2.6 V/4 V = 65%. It
is hoped that better electrocatalysts can reduce overpotentials
and increase the electrical and thermodynamic efficiency.
Debart et al.8 showed at very low current densities that the
addition of a relatively small mole percent of various transition
metal oxide particles enhances the discharge capacity, reduces
ηchg, and yet has a minimal effect on ηdis. Lu, et al.18 showed
even more dramatic positive effects of Au nanoparticles on
ηdis and of Pt nanoparticles on ηchg. It seems highly unlikely that
catalysis, i.e., the lowering of activation barriers in the electro-
chemical reaction steps, is the root cause of the observed
increase in discharge capacity. However, it is possible that
the lowering of ηchg and ηdis are true electrocatalytic effects
(although this is difficult to rationalize if insoluble reaction
products rapidly coat the catalyst particles). Hopefully, in the
future, polarization studies, i.e., measuring η(i) or i(η) can probe
the nature of the electrocatalysis in quantitative detail. Prelimin-
ary polarization studies at IBM confirm the existence of a
moderate catalytic effect for R-MnO2 in the charge current.
However, work is still in progress to determine whether R-MnO2
is in fact catalyzing the charging reaction shown in eq 2, or
catalyzing some deleterious side reactions (see below).
There is limited direct experimental evidence that the
discharge current in aprotic cells is due predominately to
eq 1. The only spectroscopic evidence is the identification of
the Li2O2 product by its Raman spectrum,6,9 although this did
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not allow quantitative comparison to the current. There is,
however, some indirect evidence for this, i.e., that the weight
gain of the cathode is consistent with what would be expected
from eq 1, based on coulometric measurements of the total
charge drawn from the battery5 and that the O2 consumption
from the gas phase is also consistent with coulometry derived
from eq 1.19 At higher discharge currents, however, there is
indirect evidence from reduced O2 consumption compared to
the coulometry that some Li2O must be formed as well.19
The identification of the charge reaction Li2O2 f 2Li þ O2
as the source of the charge current is even less definitive at this
point in time. O2 is evolved during recharge of a cathode
packed artificially with Li2O2 particles, and X-ray diffraction
studies show the disappearance of the Li2O2 from the artifi-
cially packed cathode.5 In addition, scanning electron micro-
scope (SEM) studies show the appearance of a white deposit,
presumably Li2O2, during discharge and its disappearance
during charge.6,9 While these results are certainly suggestive
that the charge current after discharge of a battery is domi-
nated by eq 2, this is far from a quantitatively settled issue.
Recent differential electrochemical mass spectrometry
(DEMS) experiments at IBM show that, while O2 is evolved
during charging of a discharged battery (especially in the
presence of some catalysts), significant oxidation products
(e.g., CO2) are also evolved.20 At the high potentials required
for charging, electrolyte oxidation and possibly even carbon
oxidation are likely and could contribute significantly to the
charging currents observed. This result also implies that the
electrochemical stability of both the electrolyte and the cathode
itself are key challenges in the development of practical Li-air
systems. In fact, we believe that electrolyte redox stability in
contact with reaction products (and intermediates) is a key
unresolved issue. Organic carbonate-based solvents such as
propylene carbonate or other carbonate mixtures have limited
anodic oxidation stability and are prone to oxidation at lower
onset potentials by typical catalytically active materials. This is
very relevant for the Li-air battery system since the oxidative
stability of the electrolyte could be reduced in the presence of
catalysts or even Li2O2. It is possible that ionic liquids may have
some advantages in this regard,21 but this remains to be seen.
This result also implies that the
electrochemical stability of both the
electrolyte and the cathode itself
are key challenges in the develop-
ment of practical Li-air systems.
The experiment in Figure 5 was done at low discharge and
charge current densities of j ≈ 0.1 mA/cm2. Figure 6 (and many
related experiments in the literature, e.g., ref 19) demonstrates
a decrease in cell capacity with increasing discharge current.
Even at 1 mA/cm2, current densities are significantly lower than
those used in typical Li-ion batteries. This cell was similar to
that described for Figure 5 except that Ketjenblack EC-600JD
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Figure 6. Discharge curves for an aprotic Li-O2 cell (based on a
Ketjenblack cathode) at three currents i: 0.1 mA., 0.5 mA, and 1 mA.
The curves give the cell output potential as a function of discharge
capacity per gram of carbon in the cathode (mAh g-1). The dashed
horizontal line is the thermodynamic standard cell potential U0. The
loss in output voltage with increasing i is highlighted by the arrow
labeled as ηdis(i), and the loss in capacity is indicated by the arrow as
capacity (i). Details of the cell are given in the text.
(Ketjenblack EC-600JD is an electroconductive carbon black and
is a product of AkzoNobel) carbon particles were used to
construct the cathode without any added catalyst particles,
and the electrolyte was 1 M LiPF6 in propylene carbonate. Note
that the discharge capacity at i = 0.1 mA in this cell is ∼3 times
higher than that for the Super P in Figure 5. There have been
many studies in the literature of the Li-O2 discharge capacity of
cathodes made from different kinds of carbon at low discharge
current densities (e.g., ref 22). There are conflicting conclusions
as to what is most important: surface area, porosity, pore
volume, and so forth.22-25 While undoubtedly all aspects are
important in some way, we believe that the more important
issue is why the low current capacity is limited to only a very
small fraction of the overall void volume.
The decrease in capacity with i has previously been discussed
in terms of an O2 transport limitation where O2 diffusion
through the cathode flooded with electrolyte cannot sustain
the electrochemical reaction rate.26,27 Thus, the electrochemical
reaction occurs in a progressively smaller region close to the
air-electrolyte interface as the current increases, possibly lead-
ing to pore clogging, which is schematically represented in
Figure 7. In principal, techniques used in PEM fuel cell cathodes
to enhance oxygen transport could also be used in Li-air
batteries. In fuel cells, a thin ion transport film covers the pores
of an otherwise O2 gas-filled cathode so that fast gas-phase O2
diffusion throughout the cathode structure is achieved. However,
cell-level transport modeling combined with measurements on
flat electrodes and flooded porous cathode cells suggests that
electron transport through the Li2O2 deposit is also an impor-
tant reason for capacity loss. This will be reported in detail
elsewhere.28 An electron conductivity issue is not surprising
since pure Li2O2 is an insulator, and its buildup during discharge
could throttle the current. Obviously, the capacity loss with i is a
serious problem in trying to obtain simultaneously high power
density and retain high gravimetric energy density.
Figure 6 also demonstrates that increasing i also reduces
battery output voltage (i.e., overpotential ηdis increases). Since
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Figure 7. Schematic representation of the air cathode and proposed
chemistry at the air cathode. Various species are as labeled in the
diagram. The left side of the diagram shows the electrolyte (with Liþ
ions), the porous carbon cathode flooded with the electrolyte, catalyst
particles, and the product Li2O2. The expanded version shows more
details of the discharge reaction in the cathode.
ηdis increases logarithmically rather than linearly with increas-
ing i,29 it is evident that the loss in output voltage is not simply
the result of an ohmic iR drop due to some internal cell resis-
tance. Rather, this implies that the charge transfer at the elec-
trodes is rate limiting and hence the principal origin of ηdis. Since
the anode reaction is known to be extremely fast, ηdis must be
related to some kinetic activation barrier in the cathode chem-
istry. The increase in ηdis with i makes achieving reasonable
power density from Li-air batteries difficult. Effective catalysts
that reduce the activation barriers for the discharge reaction
must be discovered to minimize ηdis for high i. We do note that
the use of Au nanoparticles does reduce ηdis at low i, but the
effectiveness at higher i has not yet been investigated.18
All experiments above were done at room temperature
(∼25 °C). Unpublished results by Read30 indicate that both
the capacity and output voltage (at low i) decrease significantly
with decreasing temperature in the range þ40 °C to -30 °C.
The origin of these temperature dependences is not yet under-
stood. Since propulsion batteries require a reasonable tempera-
ture range, this is an issue that will certainly require further
study.
Understanding the detailed mechanism of the electroche-
mical Li-O2 reaction and the origin of the existing overpoten-
tials is a key first step in trying to minimize overpotentials.31 In
suggesting a possible reaction path for the proposed mechan-
ism Li þ O2 T Li2O2, a few experimental facts are summarized:
(a) the product of the discharge reaction, Li2O2, is insoluble in
the aprotic solvents used (e.g., propylene carbonate), (b) after a
very brief initial transient drop in voltage, the discharge voltage
remains nearly constant throughout the discharge process until
the process terminates (Figure 5), (c) at the end of the discharge
process, mesoscale particles (∼100 nm) of Li2O2 are formed on
the carbon cathode and observed by SEM,9,19 and (d) when
using small surface area flat glassy carbon electrodes, ∼40 nm-
thick deposits electrically passivate the battery.32 These facts all
suggest that the dominant electrochemistry being observed
during discharge is that of Li2O2 formation on the surface of
Li2O2 (and its dissociation for charge).
On this basis, a mechanism31 has been suggested invol-
ving the following steps in the electrochemical oxidation of
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bulk metallic lithium:
Li T Liþ þ e - ðLi electrodeÞ

Liþ þ e - þ O2 þ  f LiO2 ðO2 cathode 1Þ

Liþ þ e - þ LiO2 f Li2 O2 ðO2 cathode 2Þ
An “*” denotes a surface site on Li2O2 where the growth
proceeds. It is essentially a neutral Li vacancy in the Li2O2
surface. The first reaction step, the dissolution of metallic
lithium into the electrolyte, is assumed to be in equilibrium.
Chemistry at the cathode is described as electrochemical
growth of Li2O2 on Li2O2 deposits. This describes all battery
chemistry except the initial nucleation of Li2O2 in the cathode
structure. Implicit in this mechanism is that there must be at
least some electrical conductivity from the carbon support
through the growing Li2O2 film to the surface. While Li2O2
itself is an insulator, the existence of neutral Li vacancies is
predicted via density functional theory (DFT) to generate
some electrical conductivity.31 Since the intermediate state
in the oxidation, LiO2* is a Li vacancy, one expects at least
some surface conductivity and perhaps even some low bulk
electrical conductivity if some of these vacancies persist in the
bulk as the film grows. However, we certainly do not anticipate
high electrical conductivity of the native electrochemically
grown Li2O2 film.
The theory of electron transfer reactions at surfaces is
complex. However, trends in electrocatalysis, where species
are strongly bound to the electrode surface, are qualitatively well
described in terms of the thermodynamics of all the surface
bound species in the electrochemical reaction steps, and DFT
gives reasonable estimates of the free energies of all surface
species and intermediates. Crystal growth generally occurs at
kinks or steps on the most stable surface. Figure 8 shows the
calculated free energy diagram for the growth at a step site on
the most stable Li2O2(100) surface.31 For this surface, the
processes described above must occur twice for it to reproduce
itself in growth. The effect of an applied potential U is included
by adding an energy, -neU, to the calculated free energy for
every intermediate with n electrons in the electrode. For U = 0,
the overall formation of Li2O2 is strongly exothermic, giving an
equilibrium potential of U0 = 2.47 V from the Nernst equation.
This value is somewhat smaller than that derived from known
standard thermodynamic data (2.96 V). At a potential U = 2.03
V, all discharge steps are downhill (ΔG e 0). Thus, the over-
potential for discharge can be qualitatively identified as ηdis =
2.47 V - 2.03 V = 0.44 V. In a similar manner, all reaction steps
are downhill (ΔG e 0) for the charge reaction at U g 3.07 V. This
gives ηchg = 3.07 V - 2.47 V = 0.60 V. While ηchg > ηdis, the
even larger asymmetry observed experimentally for the over-
potentials does not seem to be fully explained by these charge
transfer steps, and its origin is still a mystery. This is of con-
siderable importance if catalysts are to be designed to reduce the
charging overpotential. In fact, given the mechanism described
above, it is unclear how traditional electrocatalysis mechanisms
can be effective in lowering barriers when the reaction product
and intermediates are insoluble in the electrolyte.
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Figure 8. Free energy diagram calculated from DFT for the electro-
chemical reaction proposed at the cathode for the Li-air battery. Two
formula units are added during discharge (left to right) or removed
during charging (right to left). The free energies are shown at different
potentials: U = 0 is the open circuit potential, U = 2.03 V is the
highest potential for which discharge is energetically downhill for all
steps, and U = 3.07 V is the lowest potential where charging is
energetically downhill for all steps. From ref 31.
Laorie et al.33 have discussed an alternative mechanism for
the discharge reaction. Instead of the mechanism discussed
above, they suggest a disproportionation reaction of the
intermediate, i.e., LiO2* þ LiO2* f Li2O2 þ O2. However,
the free energy change ΔG for this reaction is ∼4 eV less
exorgic than the last two downhill steps, so that the dispro-
portionation mechanism is highly unlikely.
The Lithium Anode. Low specific capacity anodes, such
as LiC6, are quite acceptable for use in Li-ion batteries, as
the weight of the cathode and electrolyte dominates the
battery's overall mass and therefore energy density. However,
with lightweight Li-air cathodes replacing heavy inter-
calation cathodes, a high specific capacity of the anode
becomes much more important. Although metallic lithium
has an extraordinarily high specific capacity, various lithium
insertion/alloying materials are also possible for use as
high-capacity anodes. We discuss below some of the issues
associated with metallic lithium as the anode and then
present current research activities to help circumvent these
issues.
Lithium dendrite/moss formation upon battery cycling,
which can eventually lead to shorts between the anode and
cathode, has plagued the development of a long-lifetime sec-
ondary battery based on lithium metal.34,35 Dendrite formation
in metal plating is caused by uneven current distributions at the
metal-electrolyte interface. When lithium is immersed in an
organic solvent, it spontaneously and almost immediately
reacts to form a thin Li-ion conductive film on its surface. As
the reaction between lithium and the solvent proceeds, a
multilayer deposition of lithium salts creates a mass diffusion
barrier between the lithium and solvent, inhibiting the reaction
kinetics between the two and preventing further corrosion of
the lithium metal.16 This passivation layer is the well-known SEI
and is schematically shown in Figure 3. The chemical hetero-
geneity of the SEI can result in a brittle and morphologically
heterogeneous structure, which can accumulate defects upon
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repeated lithium stripping and plating during cycling. These
defects can produce nonuniform current distributions through-
out the SEI, leading to preferential deposition of lithium metal
and, therefore, dendrite formation.16,36,37
In order to improve the stability of the lithium anode,
several approaches involving homogeneous, highly Li-ion-
conductive artificial protective layers have been developed
to reduce dendrite formation during battery cycling. For
example, polymer electrolytes remain a promising direction
for minimizing the problems of lithium dendrite formation.
For example, Seeo, Inc. is currently developing electrolytes for
lithium metal-based batteries based on novel di- and triblock
copolymers.38 Their electrolytes combine the mechanical
stability of a hard polymer segment, such as polystyrene,
with the high Li-ion conductivity of a soft polymer segment,
such as a poly(ethylene oxide) (PEO)/Li-salt mixture. These
polymers will hopefully inhibit dendrite shorts (via mechan-
ical blocking from the hard polymer segments) while still
maintaining high ion conductivity. Alternative approaches use
Li-ion conducting glasses or ceramic materials as the solid
state electrolyte. For example, Bates et al. produced a thin film
solid state battery, based on Li/LiCoO2, and a lithium phos-
phorus oxynitride (LIPON) electrolyte that could be cycled
4000 times at low currents with only 2% lifetime capacity
fade.39 For Li-air batteries, the best results to date use thin
films of Li-ion-conducting ceramics (lithium superionic con-
ductor (LISICON)-type materials) to encase lithium metal.10
This approach is shown in Figure 3 (labeled the artificial SEI).
Generally, the Li-ion-conducting ceramic is readily reduced by
lithium metal, and therefore a thin film of a lithium stable
conducting material, e.g., Li3N or Li3P, must be inserted
between the ceramic and metal.
Another significant advantage of the ceramic based artifi-
cial SEI is that it protects the lithium metal from all atmo-
spheric contamination. An example of the remarkable barrier
properties of this type of ceramic was demonstrated by Visco
et al.,15 who successfully used this protective ceramic to
enable a primary Li-seawater battery. The strong barrier
properties of the ceramics are also essential for enabling the
aqueous, the mixed aqueous-aprotic, and the all-solid-state
electrolyte architectures of Li-air batteries discussed in sec-
tion III and Figure 2. A pure-polymer artificial SEI is unlikely to
achieve the same level of contamination protection for the
lithium for reasons discussed in section VI.
Although the ceramic Li-ion conductors offer excellent
contamination isolation of the lithium metal, they are brittle
and can only be formed reproducibly in small sheets (on the
order of a few square inches). These sheets are typically
relatively thick (on the order of a few hundred micrometers)
to instill mechanical integrity and therefore limit power
density because of the iR voltage drop at higher currents.
Thinner protective layers would lead to higher Li-ion conducti-
vity and better power densities. In addition, the brittle nature
of these materials could potentially result in barrier defects
(cracks) upon charge-discharge cycling, leading to parasitic
reactions at the anode surface. Kumar et al. have begun to
investigate ceramic polymer composites for the lithium metal
barrier in their all-solid-state Li-air battery.12 In principle,
such a composite barrier could produce advantages of both
2200 DOI: 10.1021/jz1005384 |J. Phys. Chem. Lett. 2010, 1, 2193–2203

Table 1. Physical Properties of Common Air Gases42
critical critical volume, kinetic
gas temperature, Tc [K] Vc [cm3/mol] diameter, dk [Å]
O2 154.6 73.5 3.46
N2 126.2 89.3 3.64
H2O 647 55.9 2.65
CO 134.5 90.1 3.76
CO2 304.2 91.9 3.3
polymers (excellent process ability) and ceramics (excellent
barrier properties).
Given the safety issues associated with cycling metallic
lithium-based batteries, major research efforts have focused
on producing a variety of safer anode alternatives and led to
the development of the first commercially available Li-ion
battery by Sony in 1990. Current state-of-the-art LiC6 intercala-
tion anodes have been engineered to provide very high cyclabil-
ity and safety. Similarly, insertion anodes comprised of lithium
titanate (Li4Ti5O12) have been considered for automotive appli-
cations as a result of their acceptable high-rate performance.
Furthermore, lithium titanate's lithiated and delithiated cell
structure is almost identical, making it very safe during cycling.40
Although insertion anodes exhibit reliable cyclability, their spe-
cific capacities are an order of magnitude lower than that of
metallic lithium. However, lithium alloying provides a route to
anodes with specific capacities similar to that of metallic lithium.
Unfortunately, these compounds are severely limited for prac-
tical use as a result of the dramatic volume changes associated
with the alloying process, which eventually leads to degradation
of the anode.
Li-Air vs Li-O2 Batteries: Membranes. Most experi-
ments to date on rechargeable aprotic batteries have em-
ployed O2 rather than air to avoid unwanted parasitic reac-
tions with components, such as water, carbon dioxide, carbon
monoxide, and nitrogen, in ambient air. Thus, removal of these
components remains a significant challenge that must ulti-
mately be overcome to allow Li-air battery operation for
repeated cycling and long-term use. One such method envi-
sioned to deliver O2 or highly O2-enriched gas from air to a
Li-O2 cell has been an “oxygen-diffusion” membrane that
selectively permeates O2 while retaining other gaseous spe-
cies.41 However, the incorporation of such a membrane re-
mains a critical challenge for high-rate applications, as water
vapor is much more permeable than O2 through any mem-
brane, regardless of the membrane's physical properties
(including its relative hydrophobicity).42 Table 1 presents
various physical parameters that serve as reasonable measures
of a gas's condensability (Tc) and molecular size (Vc, kinetic
diameter). Of particular interest, water molecules are much
smaller than oxygen molecules, indicating that preferential O2
permeability over water through porous membranes, where
gas separation is controlled by size exclusion mechanisms
such as Knudsen diffusion and Pouseille flow, is not possible.
Additionally, gas separation through nonporous polymeric
membranes is governed by the solution/diffusion mechanism,
where permeability of any gas through a polymer is the product
of its ability to dissolve into a polymer (i.e., its solubility) and its
ability to diffuse through the polymer (i.e., its diffusion rate).42
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In other words: P = DS, where P is a gas's permeability
coefficient through a nonporous polymer film, D is its diffusion
coefficient, and S is its solubility coefficient. For light gases, such
as those listed in Table 1.1, a gas's diffusion coefficient through
a polymer film is generally inversely correlated to its kinetic
diameter raised to a positive power, and therefore, water usually
has a higher diffusion coefficient than O2 through polymeric
membranes. Furthermore, an Arrhenius-type correlation exists
between a gas's solubilility coefficient and its condensability in
any polymer.42 As a result, water, whose condensability is much
higher than that of O2,, will also be much more soluble than O2
in any membrane. Therefore, water permeability though dense
polymer films tends to be significantly higher (sometimes many
orders of magnitude) than oxygen permeability. Nonetheless,
by preferentially permeating water instead of oxygen, mem-
branes still hold promise to deliver highly oxygen-enriched,
dehydrated air for EV applications. For example, a possible
configuration for air dehydration employs a hydrophilic mem-
brane with a very high H2O permeability compared to O2
permeability.43 As a result, O2 is retained on the high pressure
side of the membrane, where it can be sent to the battery or a
further dehydration step. Of course, the size and weight of such
a system is critical when considering the Li-air battery energy
density; however, because of water's high permeability rate, a
compact dehumidification membrane system is potentially an
attainable goal.
While preliminary experiments on Li-air batteries do
suggest the promise of being able to provide rechargeable
batteries with much higher gravimetric energy densities than
currently available, there are challenges that must be over-
come before this promise can become a reality. At present, we
limit the consideration to an aprotic liquid electrolyte since
this is the only version that has been suggested to be
electrically rechargeable.
We list below the key research that in our opinion is
necessary for the development of a practical electrically
rechargeable Li-air battery and its subsequent commerciali-
zation.
1 Quantitative understanding of the electrochemical re-
actions and their relationship to the discharge/charge
currents. This is the key to quantitatively demonstrating
chemical reversibility and understanding Coulombic
efficiency of the battery in cycling.
2 Development of oxidation-resistant electrolytes and
cathodes that can withstand high oxidation potentials
in the presence of O2. This is also essential for chemical
reversibility and Coulombic efficiency in the battery
cycling.
3 Understanding the nature of electrocatalysis for Li-air
batteries where insoluble products are formed and
the development of cost-effective catalysts to reduce
overpotentials for the discharge and charge reactions.
This is key to enhancing power density in discharge,
electrical efficiency in a discharge-charge cycle, and
ultimately in cycle life (due to possible electrolyte
oxidation).
4 Development of new nanostructured air cathodes
that optimize transport of all reactants (O2, Liþ,
and electrons) to the active catalyst surfaces and
2201 DOI: 10.1021/jz1005384 |J. Phys. Chem. Lett. 2010, 1, 2193–2203

provide appropriate space for solid lithium oxide
products. This is required to maintain capacity at
higher power densities. A new realization is that mini-
mizing difficulties due to electron transport through
the lithium oxide solid products in the cathode is
important.
5 Development of a robust lithium metal or lithium
composite electrode capable of repeated cycling at
higher current densities. This will most likely require
development of a protective layer that limits the dele-
terious effects of environmental contamination on the
lithium and inhibits dendrite growth.
6 Development of high throughput air-breathing mem-
branes (or other mechanisms) that separate O2 from
ambient air in order to avoid H2O, CO2, and other
environmental contaminants from limiting the lifetime
of Li-air batteries.
7 Understanding the origin of the temperature depend-
ences in Li-air batteries and minimizing their adverse
effects.
AUTHOR INFORMATION
Corresponding Author:
*To whom correspondence should be addressed.
Biographies
Dr. G. Girishkumar is currently an electrochemist at the IBM
Almaden Research center. He obtained his Ph.D. (2003) degree
from the Indian Institute of Science. After completion, he was
selected for a post doctoral position at the Notre Dame Radiation
Laboratory. Subsequently, he moved to Air Products and Chemical.,
Inc. as a Senior Research Scientist, (2005-2009) working in the
area of the Stabilife family of electrolyte salts for rechargeable
lithium-ion batteries. His present research focuses on electrochem-
istry of rechargeable batteries and fuel cells.
Dr. Bryan D. McCloskey joined the IBM Almaden Research
Institute as a Post-Doctoral Research Associate in 2009. He received
his B.S. at the Colorado School of Mines in 2003 and his Ph.D. in
Chemical Engineering at the University of Texas at Austin, where he
was a National Science Foundation Graduate Research Fellow in
2009. His research interests focus mainly on molecular transport
through polymer membranes.
Dr. A. C. Luntz is currently consulting with IBM Almaden on the
Battery 500 project and is also Adjunct Professor of Physics at both
the University of Southern Denmark and at Aarhus University. Prior
to this, he spent 25 years at Almaden Research Laboratory before
leaving for an academic career in Denmark in 1994. Principal
current research interests are in surface chemical dynamics, espe-
cially related to heterogeneous catalysis.
Sally A. Swanson, an advisory scientist in Nanoscale Science &
Technology, has worked for IBM Research - Almaden since 1982.
She has over 25 patents on materials for semiconductor manufac-
turing, electrophoretic and OLED displays, molecular electronics,
and lithography. Her current interests include lithium/air batteries
and DNA origami projects.
Dr. Winfried Wilcke is a Program Director at the IBM Almaden
Research Center. He holds a Ph.D. in nuclear physics, and has
worked at the University of Rochester, LBL, and Los Alamos. He
played a key role in IBM's development of supercomputers, served
as CTO of HaL (64-bit Sparc), led the IBM Icecube project, and
initiated the Battery500 lithium/air project.
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ACKNOWLEDGMENT We thankfully acknowledge all the other
members of the IBM Research Almaden and Z€ urich teams working
on Li-air batteries. Their work and discussion have contributed
greatly to the opinions expressed in this perspective. The members
are D. Bethune, M. Hart, C. Scott, B. Shelby, M. Sherwood, B. A.
Smith, C. Larson, K. Virwani, G. Wallraff, H.-C. Kim, Q. Song, and R.
Miller in San Jos

e, California and A. Curioni and T. Laino in Z€urich,
Switzerland.
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