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2010 GirisjkumarG JPCL 1 2193 2203 PDF
2010 GirisjkumarG JPCL 1 2193 2203 PDF
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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
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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
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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
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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.
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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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