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PERSPECTIVE

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

r 2010 American Chemical Society 2193 DOI: 10.1021/jz1005384 |J. Phys. Chem. Lett. 2010, 1, 2193–2203
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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
Figure 1. The gravimetric energy densities (Wh/kg) for various example, a battery with 100 kW power output at a cell voltage
types of rechargeable batteries compared to gasoline. The theore- of 2.5 V and a current density of 25 mA/cm2 will require a total
tical density is based strictly on thermodynamics and is shown as
the blue bars while the practical achievable density is indicated by internal surface area of 160 m2, equal to the internal surface of
the orange bars and numerical values. For Li-air, the practical the human lung.
value is just an estimate. For gasoline, the practical value includes One way to reduce the power density requirements is to
the average tank-to-wheel efficiency of cars. create an electric hybrid propulsion system where a small capa-
city but high power battery, for example, based on Li-ion
energy density for gasoline in Figure 1. Since the efficiency of technology, provides power for short periods of high demand,
electric propulsion systems (battery-to-wheels) are about 90%, such as during acceleration. This is possible since the ratio of
a 10-fold improvement of the current energy densities of Li-ion average-to-peak power demand in a car is only about 1:10.
batteries, which are typically between 100 and 200 Wh/kg (cell Electrical Energy Efficiency: Current Li-air cells exhibit
level), would bring electric propulsion systems on-par with large overvoltages, i.e., the charging voltage is considerably
gasoline, at least as measured by gravimetric energy density. higher than the discharge voltage. This corresponds to a
However, there is no expectation that current batteries such as low cycle electrical energy efficiency, currently on the order
Li-ion will ever come close to the target of 1700 Wh/kg. New of 60-70%. Practical propulsion batteries should exhibit
chemistries are required to achieve this goal. “round-trip” energy efficiencies of 90%. The detailed me-
The oxidation of 1 kg of lithium metal releases 11 680 Wh/kg, chanisms underlying these high over voltages are currently
not much lower than that of gasoline. This is shown as the theo- not understood, but hopefully can be substantially reduced by
retical energy density of a Li-air battery in Figure 1. However, the choice of catalysts.
practical energy densities for Li-air batteries will be far less. Liftetime and Cyclability: Current Li-air cells have been
Existing metal-air batteries, such as Zn/air, typically have a practi- demonstrated with up to about 50 cycles with only moderate
cal energy density of about 40-50% of their theoretical density. loss in capacity.5 Therefore, future research efforts need to
However, one can safely assume that even fully developed Li-air focus on improving the capacity retention during cycling.
cells will never achieve such an excellent ratio, because lithium is Nevertheless, the total number of charge cycles of large
very light, and therefore the overhead of the battery structure, propulsion batteries would not necessarily need to be high
electrolytes, and so forth will have a much larger impact. given the large energy capacity of Li-air cells. For example, a
Fortunately, an energy density of 1700 Wh/kg for the fully battery designed for a lifetime of 150 000 miles and support-
charged battery corresponds only to 14.5% of the theoretical ing a 500 mile range will need to be recharged only 300 times
energy content of lithium metal. It is not inconceivable that (full cycle equivalent). But many tons of air will have to pass
such an energy density, at the cell level, may be achievable, through a battery during its lifetime, and even minute accu-
given intensive and long-term development work. The energy mulations of moisture (for aprotic batteries) or products of
density of the complete battery system may be only half of the side reactions will be detrimental.
density realized at the cell level. Safety: The batteries of EVs will be held initially to extre-
The volumetric energy density (measured in Wh/L) of the mely high safety standards, much higher than gasoline cars.
battery is also an important design consideration. This re- Typical thermal runaway of a Li-ion battery due to overcharg-
quirement is best captured by allocating a maximum volume ing or internal shorts is not a possibility in Li-air batteries
of 300 L (family car) for the battery and its auxiliary systems. A because of the rate-limited surface nature of the reaction, i.e.,
driving range of 500 miles (800 km) requires 125 kWh the reactant O2 is not stored in the battery. However, there are
capacity (at 250 Wh/mile), thus a 300 L volume limit dictates two other safety concerns to be considered. First, the desired,
that the specific gravity of the battery, including the space though not mandatory, use of lithium metal anodes is a
allocated for air channels inside the battery and the air- well-known safety problem, since lithium metal tends to form
handling system, must not be less than 0.5 kg/L. Note that dendrites, which can short-circuit the battery and react

r 2010 American Chemical Society 2194 DOI: 10.1021/jz1005384 |J. Phys. Chem. Lett. 2010, 1, 2193–2203
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aggressively with many contaminants. Second, the presumed The battery chemistry for the all-solid-state battery is not
dominant reaction product of aprotic cells is Li2O2, which clear at this point in time, but is presumably the same as
is a strong oxidizer. Combined with an organic electrolyte, that for the aprotic electrolyte. The aprotic version was first
6
this could lead to safety issues in an accident. However, investigated by Abraham and Jiang and further developed
7 5,8,9
preliminary experiments at IBM indicate that no thermal principally by Read et al. and Bruce et al. The fully
exothermic reactions between Li2O2 and common electro- aqueous version is being developed by Polyplus,10 while the
lytes occur at temperatures below the melting point of lithium mixed electrolyte configuration is also being developed by
metal (180 °C). This safety concern does not exist in aqueous Polyplus10 and Wang and Zhou.11 A fully solid-state Li-air
cells. battery was recently reported by Kumar et al.12 Each config-
In conclusion, the requirements for large capacity auto- uration has specific advantages and presents definite scien-
motive propulsion batteries are extensive, but quite well- tific and engineering challenges, so that the ultimate choice
defined. They will serve as guidelines for the research to be for the best configuration is still an open question. A brief
carried out on Li-air systems. At present, automotive propul- preview of some of these issues is given below. While Figure 2
sion batteries are just beginning the transition from nickel and much of the discussion here assumes lithium metal as
metal hydride to Li-ion batteries, after nearly 35 years of the anode, alloy anodes are also an option for Li-air batteries
research and development on the latter. The transition to and are discussed briefly in section V.
Li-air batteries (if successful) should be viewed in terms of a In the aprotic liquid version (see Figure 2), the lithium
similar development cycle. 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
Automotive propulsion batteries perhaps Li2O) is thought to be formed via the oxygen reduc-
tion reaction (ORR). There is some evidence that, with
are just beginning the transition catalysts present, Li2O2 will undergo the oxygen evolution
from nickel metal hydride to Li-ion reaction (OER) at sufficiently high applied recharge voltages5
so that the aprotic configuration could be the basis for an
batteries, after nearly 35 years of electrically rechargeable Li-air battery. This will be discussed
research and development on the in detail later in this article. Both for the aqueous electrolyte
configuration and the mixed electrolyte configuration, the
latter. The transition to Li-air bat- cathode chemistry is identical, and there is no evidence at this
teries (if successful) should be time that the electrochemical reaction is reversible, except by
mechanically removing the reaction products and replacing
viewed in terms of a similar devel- them with fresh reactants. The great advantage of the aqueous
or mixed electrolyte configuration is that the discharge reac-
opment cycle. 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-
Architectures of Li-Air Batteries. Currently, four chemical ous and mixed systems is the development of good Li-ion con-
architectures are being pursued worldwide, which are outlined ducting membranes, which protect the anode from reacting
in Figure 2. These include three versions with liquid electrolytes: vigorously with H2O (see section V). For the aqueous system,
a fully aprotic liquid electrolyte, an aqueous electrolyte, and a
this requires the development of a lithium metal and water-
mixed system with an aqueous electrolyte immersing the
stable artificial SEIs (see Figures 2 and 3). In the mixed
cathode and an aprotic electrolyte immersing the anode. The
electrolyte system, an aprotic electrolyte is in direct contact
fourth approach is an all-solid-state battery with a solid electro-
with the lithium metal anode so that a natural SEI is formed
lyte. The fundamental electrochemistry depends upon the
on the lithium metal. This minimizes the difficult require-
electrolyte around the cathode.
ment that the membrane protecting the lithium metal from
In an aprotic electrolyte, the fundamental cathode dis-
H2O is also stable against reduction by lithium metal. Visco
charge reactions are thought to be
et al. have demonstrated an aprotic Li-air battery with an
2Li þ O2 f Li2 O2 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
and possibly humidity. The protection of lithium metal from contamination
2Li þ ð1=2ÞO2 f Li2 O is discussed in section V. All four configurations will ultimately
have to solve the difficult problem of developing a high
In an aqueous cathode electrolyte, the fundamental reac- throughput air-breathing system that passes O2 and keeps out
tions are environmental contaminants (e.g., H2O, CO2, N2). Because
2Li þ ð1=2ÞO2 þ 2Hþ f 2Liþ þ H2 O ðacidic mediaÞ only the aprotic configuration of a Li-air battery has shown
any promise of electrical rechargeability, this configuration
2Li þ ð1=2ÞO2 þ H2 O f 2LiOH ðalkaline mediaÞ has attracted the most effort worldwide to date, and we focus

r 2010 American Chemical Society 2195 DOI: 10.1021/jz1005384 |J. Phys. Chem. Lett. 2010, 1, 2193–2203
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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

r 2010 American Chemical Society 2196 DOI: 10.1021/jz1005384 |J. Phys. Chem. Lett. 2010, 1, 2193–2203
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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.
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
envisioned for the aprotic battery is a two-electron process: density. This gives the cell output voltage for discharge or the nece-
ssary applied potential for charge at the given current density as a
2Li þ O2 f Li2 O2 ðdischargeÞ ð1Þ 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
Li2 O2 f 2Li þ O2 ðchargeÞ ð2Þ directions are given by the labeled arrows in the figure. The thermo-
dynamic potential is given by the dashed line, and the overpotentials
The lithium anode is in contact with the electrolyte and forms for discharge ηdis and charge ηchg are indicated by the arrows.
a stable SEI, which protects the metal from further reaction with
the electrolyte. This is quite similar to the formation and proper- likely due to the insolubility of discharge products in the
ties of an SEI at carbon-lithium anodes in conventional Li-ion nonaqueous organic electrolyte, which causes a buildup of
batteries.16 Examples of aprotic electrolytes used to date include discharge products on the cathode surface, inhibiting the flow
organic carbonates (ethylene carbonate, propylene carbonate, of reactants (O2, Liþ, and electrons) to the active surface.
dimethyl carbonate), ethers (tetrahydrofuran (THF), dioxolane), During constant-current charging of the cell, the voltage
and esters (γ-butyrolactone), which solvate lithium salts, such as increases to approximately 4.0 V (Figure 5). Hence the charge
LiPF6, LiAsF6, LiN(SO2CF3)2, and LiSO3CF3 and have high oxida- overpotential (ηchg) is significantly greater than the discharge
tive stabilities.17 overpotential (ηdis). Thus, at present, the electrical energy effi-
A typical discharge-charge cycle of a Li-O2 cell is shown in ciency for a discharge-charge cycle is only 2.6 V/4 V = 65%. It
Figure 5, and is quite similar to others in the literature.5 The cell is hoped that better electrocatalysts can reduce overpotentials
consisted of a lithium metal foil as the anode, a 250 μm thick and increase the electrical and thermodynamic efficiency.
glass mat fiber separator, and a porous cathode constructed Debart et al.8 showed at very low current densities that the
from high surface area Super P (Super P is a conductive carbon addition of a relatively small mole percent of various transition
black and is a product of TIMCAL Graphite & Carbon) carbon metal oxide particles enhances the discharge capacity, reduces
particles mixed with R-MnO2 nanorods serving as a catalyst, ηchg, and yet has a minimal effect on ηdis. Lu, et al.18 showed
both uniformly distributed and bound to a 1.6 mm-thick even more dramatic positive effects of Au nanoparticles on
metallic nickel foam current collector with PVDF binder. ηdis and of Pt nanoparticles on ηchg. It seems highly unlikely that
The composition of the active cathode materials by weight catalysis, i.e., the lowering of activation barriers in the electro-
percent were carbon:R-MnO2:PVDF = 54:10:36. The separator chemical reaction steps, is the root cause of the observed
and cathode were flooded with 1 M LiN(SO2CF3)2 [LiTFSI] in increase in discharge capacity. However, it is possible that
propylene carbonate, which served as the electrolyte. The cell the lowering of ηchg and ηdis are true electrocatalytic effects
construction was a spring loaded Swagelok design with active (although this is difficult to rationalize if insoluble reaction
electrode areas of 1.2 cm2. The initial open circuit voltage (OCV) products rapidly coat the catalyst particles). Hopefully, in the
of this cell is ∼3.3 V, which is significantly higher than U0. This future, polarization studies, i.e., measuring η(i) or i(η) can probe
high OCV likely reflects a mixed potential effect due to inter- the nature of the electrocatalysis in quantitative detail. Prelimin-
calation of Li-ions into the R-MnO2 particles. This process ary polarization studies at IBM confirm the existence of a
terminates quickly as the cell is discharged because there is moderate catalytic effect for R-MnO2 in the charge current.
not much R-MnO2 present. Without the catalyst in the cathode, However, work is still in progress to determine whether R-MnO2
the OCV is ∼3.1 V, still slightly higher than U0 by 0.15 V. The is in fact catalyzing the charging reaction shown in eq 2, or
working voltage of this cell during discharge is approximately catalyzing some deleterious side reactions (see below).
2.6-2.7 V, which is significantly less than U0. This difference is There is limited direct experimental evidence that the
called the discharge overpotential ηdis. The discharge capacity of discharge current in aprotic cells is due predominately to
this Li-O2 cell is also much lower than its theoretical capacity eq 1. The only spectroscopic evidence is the identification of
given by the void volume of the cathode, ∼1%. This is most the Li2O2 product by its Raman spectrum,6,9 although this did

r 2010 American Chemical Society 2197 DOI: 10.1021/jz1005384 |J. Phys. Chem. Lett. 2010, 1, 2193–2203
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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, Figure 6. Discharge curves for an aprotic Li-O2 cell (based on a
presumably Li2O2, during discharge and its disappearance 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
during charge.6,9 While these results are certainly suggestive capacity per gram of carbon in the cathode (mAh g-1). The dashed
that the charge current after discharge of a battery is domi- horizontal line is the thermodynamic standard cell potential U0. The
nated by eq 2, this is far from a quantitatively settled issue. loss in output voltage with increasing i is highlighted by the arrow
Recent differential electrochemical mass spectrometry 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.
(DEMS) experiments at IBM show that, while O2 is evolved
during charging of a discharged battery (especially in the (Ketjenblack EC-600JD is an electroconductive carbon black and
presence of some catalysts), significant oxidation products is a product of AkzoNobel) carbon particles were used to
(e.g., CO2) are also evolved.20 At the high potentials required construct the cathode without any added catalyst particles,
for charging, electrolyte oxidation and possibly even carbon and the electrolyte was 1 M LiPF6 in propylene carbonate. Note
oxidation are likely and could contribute significantly to the that the discharge capacity at i = 0.1 mA in this cell is ∼3 times
charging currents observed. This result also implies that the higher than that for the Super P in Figure 5. There have been
electrochemical stability of both the electrolyte and the cathode many studies in the literature of the Li-O2 discharge capacity of
itself are key challenges in the development of practical Li-air cathodes made from different kinds of carbon at low discharge
systems. In fact, we believe that electrolyte redox stability in current densities (e.g., ref 22). There are conflicting conclusions
contact with reaction products (and intermediates) is a key as to what is most important: surface area, porosity, pore
unresolved issue. Organic carbonate-based solvents such as volume, and so forth.22-25 While undoubtedly all aspects are
propylene carbonate or other carbonate mixtures have limited important in some way, we believe that the more important
anodic oxidation stability and are prone to oxidation at lower issue is why the low current capacity is limited to only a very
onset potentials by typical catalytically active materials. This is small fraction of the overall void volume.
very relevant for the Li-air battery system since the oxidative The decrease in capacity with i has previously been discussed
stability of the electrolyte could be reduced in the presence of in terms of an O2 transport limitation where O2 diffusion
catalysts or even Li2O2. It is possible that ionic liquids may have through the cathode flooded with electrolyte cannot sustain
some advantages in this regard,21 but this remains to be seen. 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-
This result also implies that the ing to pore clogging, which is schematically represented in
Figure 7. In principal, techniques used in PEM fuel cell cathodes
electrochemical stability of both the to enhance oxygen transport could also be used in Li-air
batteries. In fuel cells, a thin ion transport film covers the pores
electrolyte and the cathode itself of an otherwise O2 gas-filled cathode so that fast gas-phase O2
are key challenges in the develop- diffusion throughout the cathode structure is achieved. However,
cell-level transport modeling combined with measurements on
ment of practical Li-air systems. 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
The experiment in Figure 5 was done at low discharge and elsewhere.28 An electron conductivity issue is not surprising
charge current densities of j ≈ 0.1 mA/cm2. Figure 6 (and many since pure Li2O2 is an insulator, and its buildup during discharge
related experiments in the literature, e.g., ref 19) demonstrates could throttle the current. Obviously, the capacity loss with i is a
a decrease in cell capacity with increasing discharge current. serious problem in trying to obtain simultaneously high power
Even at 1 mA/cm2, current densities are significantly lower than density and retain high gravimetric energy density.
those used in typical Li-ion batteries. This cell was similar to Figure 6 also demonstrates that increasing i also reduces
that described for Figure 5 except that Ketjenblack EC-600JD battery output voltage (i.e., overpotential ηdis increases). Since

r 2010 American Chemical Society 2198 DOI: 10.1021/jz1005384 |J. Phys. Chem. Lett. 2010, 1, 2193–2203
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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
Figure 7. Schematic representation of the air cathode and proposed
chemistry at the air cathode. Various species are as labeled in the chemistry except the initial nucleation of Li2O2 in the cathode
diagram. The left side of the diagram shows the electrolyte (with Liþ structure. Implicit in this mechanism is that there must be at
ions), the porous carbon cathode flooded with the electrolyte, catalyst least some electrical conductivity from the carbon support
particles, and the product Li2O2. The expanded version shows more
details of the discharge reaction in the cathode. 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
ηdis increases logarithmically rather than linearly with increas-
ing i,29 it is evident that the loss in output voltage is not simply some electrical conductivity.31 Since the intermediate state
the result of an ohmic iR drop due to some internal cell resis- in the oxidation, LiO2* is a Li vacancy, one expects at least
tance. Rather, this implies that the charge transfer at the elec- some surface conductivity and perhaps even some low bulk
trodes is rate limiting and hence the principal origin of ηdis. Since electrical conductivity if some of these vacancies persist in the
the anode reaction is known to be extremely fast, ηdis must be bulk as the film grows. However, we certainly do not anticipate
related to some kinetic activation barrier in the cathode chem- high electrical conductivity of the native electrochemically
istry. The increase in ηdis with i makes achieving reasonable grown Li2O2 film.
power density from Li-air batteries difficult. Effective catalysts The theory of electron transfer reactions at surfaces is
that reduce the activation barriers for the discharge reaction complex. However, trends in electrocatalysis, where species
must be discovered to minimize ηdis for high i. We do note that are strongly bound to the electrode surface, are qualitatively well
the use of Au nanoparticles does reduce ηdis at low i, but the described in terms of the thermodynamics of all the surface
effectiveness at higher i has not yet been investigated.18 bound species in the electrochemical reaction steps, and DFT
All experiments above were done at room temperature gives reasonable estimates of the free energies of all surface
(∼25 °C). Unpublished results by Read30 indicate that both species and intermediates. Crystal growth generally occurs at
the capacity and output voltage (at low i) decrease significantly kinks or steps on the most stable surface. Figure 8 shows the
with decreasing temperature in the range þ40 °C to -30 °C. calculated free energy diagram for the growth at a step site on
The origin of these temperature dependences is not yet under- the most stable Li2O2(100) surface.31 For this surface, the
stood. Since propulsion batteries require a reasonable tempera- processes described above must occur twice for it to reproduce
ture range, this is an issue that will certainly require further itself in growth. The effect of an applied potential U is included
study. by adding an energy, -neU, to the calculated free energy for
Understanding the detailed mechanism of the electroche- every intermediate with n electrons in the electrode. For U = 0,
mical Li-O2 reaction and the origin of the existing overpoten- the overall formation of Li2O2 is strongly exothermic, giving an
tials is a key first step in trying to minimize overpotentials.31 In equilibrium potential of U0 = 2.47 V from the Nernst equation.
suggesting a possible reaction path for the proposed mechan-
This value is somewhat smaller than that derived from known
ism Li þ O2 T Li2O2, a few experimental facts are summarized:
standard thermodynamic data (2.96 V). At a potential U = 2.03
(a) the product of the discharge reaction, Li2O2, is insoluble in
V, all discharge steps are downhill (ΔG e 0). Thus, the over-
the aprotic solvents used (e.g., propylene carbonate), (b) after a
potential for discharge can be qualitatively identified as ηdis =
very brief initial transient drop in voltage, the discharge voltage
remains nearly constant throughout the discharge process until 2.47 V - 2.03 V = 0.44 V. In a similar manner, all reaction steps
the process terminates (Figure 5), (c) at the end of the discharge are downhill (ΔG e 0) for the charge reaction at U g 3.07 V. This
process, mesoscale particles (∼100 nm) of Li2O2 are formed on gives ηchg = 3.07 V - 2.47 V = 0.60 V. While ηchg > ηdis, the
the carbon cathode and observed by SEM,9,19 and (d) when even larger asymmetry observed experimentally for the over-
using small surface area flat glassy carbon electrodes, ∼40 nm- potentials does not seem to be fully explained by these charge
thick deposits electrically passivate the battery.32 These facts all transfer steps, and its origin is still a mystery. This is of con-
suggest that the dominant electrochemistry being observed siderable importance if catalysts are to be designed to reduce the
during discharge is that of Li2O2 formation on the surface of charging overpotential. In fact, given the mechanism described
Li2O2 (and its dissociation for charge). above, it is unclear how traditional electrocatalysis mechanisms
On this basis, a mechanism31 has been suggested invol- can be effective in lowering barriers when the reaction product
ving the following steps in the electrochemical oxidation of and intermediates are insoluble in the electrolyte.

r 2010 American Chemical Society 2199 DOI: 10.1021/jz1005384 |J. Phys. Chem. Lett. 2010, 1, 2193–2203
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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,
Figure 8. Free energy diagram calculated from DFT for the electro- such as a poly(ethylene oxide) (PEO)/Li-salt mixture. These
chemical reaction proposed at the cathode for the Li-air battery. Two polymers will hopefully inhibit dendrite shorts (via mechan-
formula units are added during discharge (left to right) or removed ical blocking from the hard polymer segments) while still
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 maintaining high ion conductivity. Alternative approaches use
highest potential for which discharge is energetically downhill for all Li-ion conducting glasses or ceramic materials as the solid
steps, and U = 3.07 V is the lowest potential where charging is state electrolyte. For example, Bates et al. produced a thin film
energetically downhill for all steps. From ref 31. solid state battery, based on Li/LiCoO2, and a lithium phos-
phorus oxynitride (LIPON) electrolyte that could be cycled
Laorie et al.33 have discussed an alternative mechanism for 4000 times at low currents with only 2% lifetime capacity
the discharge reaction. Instead of the mechanism discussed fade.39 For Li-air batteries, the best results to date use thin
above, they suggest a disproportionation reaction of the films of Li-ion-conducting ceramics (lithium superionic con-
intermediate, i.e., LiO2* þ LiO2* f Li2O2 þ O2. However, ductor (LISICON)-type materials) to encase lithium metal.10
the free energy change ΔG for this reaction is ∼4 eV less This approach is shown in Figure 3 (labeled the artificial SEI).
exorgic than the last two downhill steps, so that the dispro- Generally, the Li-ion-conducting ceramic is readily reduced by
portionation mechanism is highly unlikely. lithium metal, and therefore a thin film of a lithium stable
The Lithium Anode. Low specific capacity anodes, such conducting material, e.g., Li3N or Li3P, must be inserted
as LiC6, are quite acceptable for use in Li-ion batteries, as between the ceramic and metal.
the weight of the cathode and electrolyte dominates the Another significant advantage of the ceramic based artifi-
battery's overall mass and therefore energy density. However, cial SEI is that it protects the lithium metal from all atmo-
with lightweight Li-air cathodes replacing heavy inter- spheric contamination. An example of the remarkable barrier
calation cathodes, a high specific capacity of the anode properties of this type of ceramic was demonstrated by Visco
becomes much more important. Although metallic lithium et al.,15 who successfully used this protective ceramic to
has an extraordinarily high specific capacity, various lithium enable a primary Li-seawater battery. The strong barrier
insertion/alloying materials are also possible for use as properties of the ceramics are also essential for enabling the
high-capacity anodes. We discuss below some of the issues aqueous, the mixed aqueous-aprotic, and the all-solid-state
associated with metallic lithium as the anode and then electrolyte architectures of Li-air batteries discussed in sec-
present current research activities to help circumvent these tion III and Figure 2. A pure-polymer artificial SEI is unlikely to
issues. achieve the same level of contamination protection for the
Lithium dendrite/moss formation upon battery cycling, lithium for reasons discussed in section VI.
which can eventually lead to shorts between the anode and Although the ceramic Li-ion conductors offer excellent
cathode, has plagued the development of a long-lifetime sec- contamination isolation of the lithium metal, they are brittle
ondary battery based on lithium metal.34,35 Dendrite formation and can only be formed reproducibly in small sheets (on the
in metal plating is caused by uneven current distributions at the order of a few square inches). These sheets are typically
metal-electrolyte interface. When lithium is immersed in an relatively thick (on the order of a few hundred micrometers)
organic solvent, it spontaneously and almost immediately to instill mechanical integrity and therefore limit power
reacts to form a thin Li-ion conductive film on its surface. As density because of the iR voltage drop at higher currents.
the reaction between lithium and the solvent proceeds, a Thinner protective layers would lead to higher Li-ion conducti-
multilayer deposition of lithium salts creates a mass diffusion vity and better power densities. In addition, the brittle nature
barrier between the lithium and solvent, inhibiting the reaction of these materials could potentially result in barrier defects
kinetics between the two and preventing further corrosion of (cracks) upon charge-discharge cycling, leading to parasitic
the lithium metal.16 This passivation layer is the well-known SEI reactions at the anode surface. Kumar et al. have begun to
and is schematically shown in Figure 3. The chemical hetero- investigate ceramic polymer composites for the lithium metal
geneity of the SEI can result in a brittle and morphologically barrier in their all-solid-state Li-air battery.12 In principle,
heterogeneous structure, which can accumulate defects upon such a composite barrier could produce advantages of both

r 2010 American Chemical Society 2200 DOI: 10.1021/jz1005384 |J. Phys. Chem. Lett. 2010, 1, 2193–2203
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Table 1. Physical Properties of Common Air Gases42 In other words: P = DS, where P is a gas's permeability
coefficient through a nonporous polymer film, D is its diffusion
critical critical volume, kinetic coefficient, and S is its solubility coefficient. For light gases, such
gas temperature, Tc [K] Vc [cm3/mol] diameter, dk [Å]
as those listed in Table 1.1, a gas's diffusion coefficient through
O2 154.6 73.5 3.46 a polymer film is generally inversely correlated to its kinetic
N2 126.2 89.3 3.64 diameter raised to a positive power, and therefore, water usually
H2O 647 55.9 2.65 has a higher diffusion coefficient than O2 through polymeric
CO 134.5 90.1 3.76 membranes. Furthermore, an Arrhenius-type correlation exists
CO2 304.2 91.9 3.3 between a gas's solubilility coefficient and its condensability in
any polymer.42 As a result, water, whose condensability is much
polymers (excellent process ability) and ceramics (excellent higher than that of O2,, will also be much more soluble than O2
barrier properties). in any membrane. Therefore, water permeability though dense
Given the safety issues associated with cycling metallic polymer films tends to be significantly higher (sometimes many
lithium-based batteries, major research efforts have focused orders of magnitude) than oxygen permeability. Nonetheless,
on producing a variety of safer anode alternatives and led to by preferentially permeating water instead of oxygen, mem-
the development of the first commercially available Li-ion branes still hold promise to deliver highly oxygen-enriched,
battery by Sony in 1990. Current state-of-the-art LiC6 intercala- dehydrated air for EV applications. For example, a possible
tion anodes have been engineered to provide very high cyclabil- configuration for air dehydration employs a hydrophilic mem-
ity and safety. Similarly, insertion anodes comprised of lithium brane with a very high H2O permeability compared to O2
titanate (Li4Ti5O12) have been considered for automotive appli- permeability.43 As a result, O2 is retained on the high pressure
cations as a result of their acceptable high-rate performance. side of the membrane, where it can be sent to the battery or a
Furthermore, lithium titanate's lithiated and delithiated cell further dehydration step. Of course, the size and weight of such
structure is almost identical, making it very safe during cycling.40 a system is critical when considering the Li-air battery energy
Although insertion anodes exhibit reliable cyclability, their spe- density; however, because of water's high permeability rate, a
cific capacities are an order of magnitude lower than that of compact dehumidification membrane system is potentially an
metallic lithium. However, lithium alloying provides a route to attainable goal.
anodes with specific capacities similar to that of metallic lithium. While preliminary experiments on Li-air batteries do
Unfortunately, these compounds are severely limited for prac- suggest the promise of being able to provide rechargeable
tical use as a result of the dramatic volume changes associated batteries with much higher gravimetric energy densities than
with the alloying process, which eventually leads to degradation currently available, there are challenges that must be over-
of the anode. come before this promise can become a reality. At present, we
Li-Air vs Li-O2 Batteries: Membranes. Most experi- limit the consideration to an aprotic liquid electrolyte since
ments to date on rechargeable aprotic batteries have em- this is the only version that has been suggested to be
ployed O2 rather than air to avoid unwanted parasitic reac- electrically rechargeable.
tions with components, such as water, carbon dioxide, carbon We list below the key research that in our opinion is
monoxide, and nitrogen, in ambient air. Thus, removal of these necessary for the development of a practical electrically
components remains a significant challenge that must ulti- rechargeable Li-air battery and its subsequent commerciali-
mately be overcome to allow Li-air battery operation for zation.
repeated cycling and long-term use. One such method envi- 1 Quantitative understanding of the electrochemical re-
sioned to deliver O2 or highly O2-enriched gas from air to a actions and their relationship to the discharge/charge
Li-O2 cell has been an “oxygen-diffusion” membrane that currents. This is the key to quantitatively demonstrating
selectively permeates O2 while retaining other gaseous spe- chemical reversibility and understanding Coulombic
cies.41 However, the incorporation of such a membrane re- efficiency of the battery in cycling.
mains a critical challenge for high-rate applications, as water 2 Development of oxidation-resistant electrolytes and
vapor is much more permeable than O2 through any mem- cathodes that can withstand high oxidation potentials
brane, regardless of the membrane's physical properties in the presence of O2. This is also essential for chemical
(including its relative hydrophobicity).42 Table 1 presents reversibility and Coulombic efficiency in the battery
various physical parameters that serve as reasonable measures cycling.
of a gas's condensability (Tc) and molecular size (Vc, kinetic 3 Understanding the nature of electrocatalysis for Li-air
diameter). Of particular interest, water molecules are much batteries where insoluble products are formed and
smaller than oxygen molecules, indicating that preferential O2 the development of cost-effective catalysts to reduce
permeability over water through porous membranes, where overpotentials for the discharge and charge reactions.
gas separation is controlled by size exclusion mechanisms This is key to enhancing power density in discharge,
such as Knudsen diffusion and Pouseille flow, is not possible. electrical efficiency in a discharge-charge cycle, and
Additionally, gas separation through nonporous polymeric ultimately in cycle life (due to possible electrolyte
membranes is governed by the solution/diffusion mechanism, oxidation).
where permeability of any gas through a polymer is the product 4 Development of new nanostructured air cathodes
of its ability to dissolve into a polymer (i.e., its solubility) and its that optimize transport of all reactants (O2, Liþ,
ability to diffuse through the polymer (i.e., its diffusion rate).42 and electrons) to the active catalyst surfaces and

r 2010 American Chemical Society 2201 DOI: 10.1021/jz1005384 |J. Phys. Chem. Lett. 2010, 1, 2193–2203
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provide appropriate space for solid lithium oxide ACKNOWLEDGMENT We thankfully acknowledge all the other
products. This is required to maintain capacity at members of the IBM Research Almaden and Z€ urich teams working
higher power densities. A new realization is that mini- on Li-air batteries. Their work and discussion have contributed
mizing difficulties due to electron transport through greatly to the opinions expressed in this perspective. The members
the lithium oxide solid products in the cathode is 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.
important.
Miller in San Jos
e, California and A. Curioni and T. Laino in Z€urich,
5 Development of a robust lithium metal or lithium Switzerland.
composite electrode capable of repeated cycling at
higher current densities. This will most likely require
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