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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 capacity 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 mechanisms 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 supporting 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 accumulations of moisture (for aprotic batteries) or products of
side reactions will be detrimental.
Safety: The batteries of EVs will be held initially to extremely high safety standards, much higher than gasoline cars.
Typical thermal runaway of a Li-ion battery due to overcharging 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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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.
Figure 3. Schematic drawing of the lithium metal-electrolyte interface choices. Both the complicated natural SEI formed by reduction
of the electrolyte and an artificial SEI, e.g., Li-ion-conducting ceramic,
are shown as examples. Adapted from refs 14 and 15.
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charge
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Li electrode
O2 cathode 1
Li e - LiO2 f Li2 O2
O2 cathode 2
Li e - O2 f LiO2
dis increases logarithmically rather than linearly with increasing 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 resistance. Rather, this implies that the charge transfer at the electrodes is rate limiting and hence the principal origin of dis. Since
the anode reaction is known to be extremely fast, dis must be
related to some kinetic activation barrier in the cathode chemistry. The increase in dis 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 dis for high i. We do note that
the use of Au nanoparticles does reduce dis 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 40 C to -30 C.
The origin of these temperature dependences is not yet understood. Since propulsion batteries require a reasonable temperature range, this is an issue that will certainly require further
study.
Understanding the detailed mechanism of the electrochemical Li-O2 reaction and the origin of the existing overpotentials is a key first step in trying to minimize overpotentials.31 In
suggesting a possible reaction path for the proposed mechanism Li 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 nmthick 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 involving the following steps in the electrochemical oxidation of
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Figure 8. Free energy diagram calculated from DFT for the electrochemical 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.
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critical volume,
Vc [cm3/mol]
kinetic
diameter, dk []
O2
N2
154.6
126.2
73.5
89.3
3.46
3.64
gas
H2O
647
55.9
2.65
CO
134.5
90.1
3.76
CO2
304.2
91.9
3.3
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REFERENCES
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AUTHOR INFORMATION
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Corresponding Author:
*To whom correspondence should be addressed.
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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 electrochemistry 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, especially 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 manufacturing, 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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