The lithium-ion charge is on
The lithium-ion
charge is on
E ven though the internal-combustion
engine will for the foreseeable fu-
ture remain the principal powerplant
for car and truck propulsion, in the long
term electric-drive technology is the key
to environmentally sustainable road
transportation. Electric power means
batteries, of course, and as anyone who
uses a mobile phone or laptop computer
knows, current electrochemical energy-
storage systems often leave much to be
desired in terms of energy density and
capacity. The limitations of large-format,
high-power batteries for vehicles are
even more severe.
Such is the case because functional
batteries are “boxes of technical trade-
offs and compromises,” as one noted
battery expert puts it. Maximization of
nearly any important performance char-
acteristic or feature nearly always re-
sults in the diminution of another. Right
now, scientists and engineers are wres-
tling with the many interrelated techni-
cal factors that determine battery per-
formance to produce “Goldilocks” sys-
tems with properties optimized to be
28 JULY 2009 aei
Multiple engineering trade-offs define the
capabilities and limitations of the latest lithium-
ion batteries for next-generation hybrid, plug-in,
and pure-electric vehicles.
by Steven Ashley
“just right” for powering the hybrid- and cycle life, have in large part ad-
electric (HEV), plug-in hybrid electric dressed earlier concerns with calendar
(PHEV) and, eventually, pure-electric life at elevated storage temperatures
(EV) vehicles. The quest for truly effec- and tolerance to abuse. Along with the
tive energy storage for electric-drive expectations of significantly lower costs
technology, though promising, will have as production volumes rise, this con-
to continue for many years to come. tinuing evolution should lead to the rise
Still, that there has been progress in of PHEVs in the coming decade. In the
rechargeable battery technology is un- meantime, provisions in the recent
deniable. Nickel metal-hydride (NiMH) Congressional stimulus bill for billions
batteries, which only became well-es- of dollars of support for advanced-bat-
tablished during the past few years, will tery development and manufacturing
help power about a million newly built facilities and the installation of electric-
hybrid vehicles in 2010 globally, accord- grid storage capabilities to enable wider
ing to market forecasts. And recent de- use of renewable energy could help
velopments in lithium-ion cell technol- jump-start a new, multibillion-dollar
ogy, which offers superior performance business in the U.S. On the other hand,
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The Ford Escape Plug-in Hybrid SUV, which can travel from 30 to 40 mi (48 to 64 km) solely
on electricity from a rechargeable lithium-ion battery pack, is part of a demonstration
fleet the company is developing in a partnership with Southern California Edison and the
Electric Power Research Institute.
industry observers said that advanced
battery technology for fully capable
EVs—full size, affordable, and long
range—will have to wait for fundamen-
tal breakthroughs in electrochemistry.
Automotive Li-ion nears maturity
“Technical feasibility for Li-ion batter-
ies for PHEVs is essentially here,” said
Patrick B. Davis, Program Manager for
Vehicle Technologies, Energy
Efficiency, and Renewable Energy, U.S.
Department of Energy. He added that
“we also have a road map for reducing
battery costs for PHEVs to current mar-
ket levels, placing us at the same stage
that HEV batteries were a few years
ago.”
However, cautioned Richard
Doisneau, Chief Technology Officer of
the Saft Battery Group in Bagnolet,
France, “We must be humble and admit
that large-format vehicular battery tech-
nology is not yet fully mature. Many
desirable characteristics for a battery are
to some extent contradictory.” Greater
energy density means greater safety
countermeasures required, for example.
“I’m appalled when I hear somebody
say, ‘My product is absolutely safe.’ All
Li-ion electrolyte solvents can burn and,
if great care is not taken, the ingredients
for fire can be present—high voltage,
heat, fuel, and oxygen.”
Beyond safety, “cost is the number
one driver, which in large part comes
down to cell and battery pack manufac-
aei-online.org
turability,” Doisneau continued. Also
high in the OEM requirement matrix are
parameters such as performance (power
and energy capacity, or specific output);
volume; mass; thermal operating char-
acteristics; shock, vibration, and envi-
ronmental resistance; calendar life; and
cycle life. Of the last factor, he said: “No
one can truly demonstrate long-term
calendar life with certainty since accel-
erated aging tests inherently involve
significant error.” Given the complexi-
ties, therefore, “What’s most important
for vehicular batteries is very close co-
operation with the car maker right from
the start of the project,” Doisneau con-
cluded. “An easy, drop-in solution does
not exist.”
The current worldwide market for
vehicular batteries is from $700 million
to $800 million a year, according to
Menahem Anderman, President of Total
Battery Consulting Inc. of Oregon
House, CA. Not including prototype
battery and research projects, Panasonic
EV Energy Co., a joint venture between
Toyota Motor Corp. and Matsushita
Electric Industrial Co., today holds an
80% market share for NiMH batteries,
with Sanyo in the second position, and
Matsushita itself in third. Other battery
makers account for about 3% of total
production. Li-ion batteries, which first
hit the vehicle market in 2008, make up
less than 1%—“a few hundred units.”
Other manufacturers of advanced bat-
teries include A123Systems, Altair
Energy/Environment
Feature
EnerDel’s proprietary lithium-ion battery
cells, shown stacked inside this 23-kg (51-lb)
battery pack of 15 L (915 in3), feature anodes
composed of titanium oxide and cathodes of
manganese oxide.
Nanotechnologies, Johnson Controls-
Saft Advanced Power Solutions, E-One
Moli Energy, Electrovaya, EnerDel,
NEC, and Valence Technology.
Anderman expects Li-ion production
“to rise to a few thousand units in 2009
and, if things go well, to reach perhaps
10,000 units annually by 2012.”
Different batteries,
different applications
Each class of electric-drive vehicle has a
different performance requirement, ex-
plained David Howell, Manager of
Electrochemical Energy Storage R&D at
the DOE. “HEVs need high power in
short pulses, from 1.0 to 1.5 kW·h,
which means the batteries must be ca-
pable of many shallow charging cycles,”
he said. Current NiMH battery packs
cost from $1200 to $1800, “so the short-
term goal for Li-ion is a similar, com-
petitive price, with a long-term target of
$500 apiece, both based on production
of 100,000 units a year.”
PHEVs require a larger battery that
can provide energy in all-electric mode
for a defined distance, Howell contin-
ued. “For a 10-mi electric range, a PHEV
needs 5 kW·h of usable energy, and for
40 mi 10 kW·h,” he said. But it also has
to provide higher continuous-power
discharge—deep charge cycles more
like those of an EV. Then, in addition,
they must be capable of many shallow
cycles for hybrid operational mode. “We
estimate that right now the cost of most
aei JULY 2009 29
 Machine operators at Saft’s lithium-ion
automotive battery manufacturing facility in
The lithium-ion charge is on Nersac, France, complete a quality check at
the end of the coating line, where positive
and negative electrode films are applied to
conductive metal foils on rollers.
suitable Li-ion batteries is about $1000
per kW·h.” By 2012, say DOE cost mod-
els, the cost should drop to $500 per
kW·h and, ultimately, to $300 per kW·h.
To accomplish their even more dif-
ficult functions, “EV batteries need to
produce about 40 kW·h of continuous-
discharge energy and be capable of one
charge each week,” Howell said. “But
no current battery can do that now be-
cause of significant technical challenges.”
DOE cost goals for future EV batteries is
$150 per kW·h. By comparison, today’s
consumer-electronics batteries go for
about $250 per kW·h.

Li-ion chemistry
Next-generation HEVs and the new
PHEVs will use Li-ion technology, the
battery chemistry that today provides
energy for a majority of consumer-elec-
tronics applications following Sony’s
commercial introduction of the technol-
ogy in 1991. Li-ion cells are typically
based on an anode made of graphitic
Saft, Didier Cocatrix

carbon and a cathode of layered (a two-

dimensional structure) metal oxide, said
M. Stanley Whittingham, who many
experts consider to be the father of Li-
ion batteries. Li-ion technology, said the
Professor of chemistry and materials
science at Binghamton University in
New York, relies on “the relative ease
with which lithium ions can move in
and out of the electrodes without
changing their molecular structure (and
thus volume)—a process known as in-
tercalation.” An organic carbonate sol-
vent serves as the liquid electrolyte—the
medium that carries internal charge be-
tween the electrodes—for these cells, he
said.
Whittingham pointed out that fear of
a growing scarcity of lithium metal from
producing countries such as Bolivia,
China, and Russia is a red herring. The
DOE, he reported, “says that there will
be no problem with lithium supply until
at least 2050, and by then widespread
battery recycling will be in force.” In
fact, market shortfalls of nickel and co-
balt supplies may turn out to have a
great impact on price and production
levels of various battery types.
Li-ion battery technology variants,
generally distinguished by the material
used for the cathode, are being studied,
said Gary Henricksen, Manager of
Electrochemical Energy Storage at
Argonne National Laboratory. Several
manufacturers, such as Johnson
Controls, Saft, and Panasonic, today
believe that a formulation of nickel
(80%), cobalt (15%), and aluminum (5%)
is the best compromise, “but that could
easily change over the next few years,”
he said. This NCA chemistry is “ther-
mally most difficult to control because it
is exothermically reactive at a high state
of charge, which can lead to combus-
tion,” Henricksen explained. “If over-
charged, an NCA cell can generate heat
and start releasing oxygen at the elec-
trode.” The combination of high volt-
age, heat, a flammable electrolyte, and
oxygen constitutes a potential fire haz-
ard. But with sufficient thermal controls,
NCA systems avoid so-called thermal
runaway. NCA systems will be used in
the new Mercedes-Benz S-Class mild
hybrid, the BMW 7 Series hybrid,
Toyota and Ford’s PHEV prototypes,
and a hybrid delivery vehicle from
Azure Dynamics.
An alternative to a Li-ion cell is
based on a manganese-oxide (or spinel)
cathode, which Henricksen said releases
less oxygen at higher charge states.
Manganese oxide based batteries suffer,
however, when the manganese metal
dissolves into the organic electrolyte,
reducing battery capacity. The leading
proponent of this battery chemistry is
Korea’s LG Chem; another is EnerDel, a
subsidiary of Indiana-based Ener1.
According to Mohamed Alamgir,
Director of Research at Compact Power,
LG Chem’s U.S. supplier of vehicular
batteries, the manganese-based cathode
chemistry contains additives to improve
calendar life under high-temperature
conditions. The cells also feature special
temperature-resistant separators (the
membranes between the electrodes) that
are mechanically reinforced to better
withstand internal electrical shorts and
overcharges.
Even better safety is offered by a bat-
tery chemistry founded on iron-phos-
phate cathodes, which produce no oxy-
gen at high states of charge, Argonne’s
Henricksen said. “Unfortunately, iron
phosphate isn’t very conductive,” which
cuts the resulting cell’s voltage and lim-
its battery capacity. Researchers at
A123Systems of Cambridge, MA, fabri-
cate cathodes from a powder-like pre-
cursor of iron-phosphate particles that
are smaller than 100 nm (3.94 µm) in

30 JULY 2009 aei aei-online.org


size, explained Yet-Ming Chang,
Materials Science Professor at the
Massachusetts Institute of Technology
and A123 co-founder. Beyond applica-
tions in hybrid buses from Daimler AG
and EVs from Think, he said, the iron-
phosphate chemistry is being employed
in a special cell optimized for ultra-high
power output. The cell, which was in-
troduced this year in the kinetic-energy
recovery system (KERS) in the McLaren
Formula One car driven by Lewis
Hamilton, is charged by regenerative
braking energy and “provides 6 or 7 s of
boost when engaged.”
Yet another variation on the Li-ion
theme is a battery with an anode made
of lithium-titanium oxide (LTO), which
was developed by Ener1 in collabora-
tion with Argonne Lab, said
Henricksen. Use of LTO in the anode
rather than graphite reduces the possi-
bility of runaway thermal events de-
rived from anode reactions (as opposed
to the more severe ones at the cathode)
and extends battery life. Whereas
graphite may experience up to a 9%
change in volume caused by microstruc-
tural alterations as electrical charges
aei-online.org
LG Chem/Compact Power uses highly
automated fabrication lines to mass-
produce manganese oxide-based
lithium-ion cells, which helps keep
manufacturing costs down.
enter and exit the material over the life
of a battery, LTO hardly changes at all.
The company produces Li-ion batteries
for Think.
Mass production
It is generally agreed that manufacturing
is the key to cutting battery costs. In this
area, Japanese firms hold a clear advan-
tage, having for years produced Li-ion
batteries for consumer electronics appli-
cations in volumes constituting billions
of cells. Standard cell design involves
long, thin electrodes that are wound
together and placed in metal enclosures
filled with electrolyte. Japanese makers
are working on their fourth or fifth gen-
erations of automated manufacturing
processes, said battery consultant
Anderman.
Although prior practice had been to
fabricate larger, high-power cells in the
familiar metal cans (both cylindrical and
prismatic in shape), companies such as
LG Chem, NEC, and EnerDel more re-
cently begun to fabricate cells using
laminated metal-polymer film packag-
ing. Manufacture of the earlier can for-
mat involves “laborious winding of
long strips of cathode, anode, and sepa-
rator materials,” said Compact Power’s
Alamgir, who went on to describe his
firm’s proprietary “stack-and-fold de-
sign, an adaptation of our consumer
electronics process that is considerably
easier to scale up.” The laminated
packaging is especially suitable for
plate-type electrodes and involves far
fewer parts than its metal counterpart, so
that it has advantages both with respect
to manufacturing and cost, he added.
Fabrication of the plate-type cath-
odes and anodes involves coating cop-
Energy/Environment
Feature
per foil with the precursor electrode
materials—graphite, metal oxide, bind-
ers—in powder form, Alamgir ex-
plained. The electrodes enter a slitting
machine, which calenders and sizes
them to the desired dimensions.
Automated equipment next stacks the
thin electrode plates with the polymer
separators in between. The stacks are
placed in individual laminated polymer
and metal film packages, which are then
filled with electrolyte and sealed. Then
the cells are subjected to a so-called for-
mation step in which they are charged
for the first time and tested. Assembly
into a battery packs follows.
Although recent U.S. government
funding for the development of a do-
mestic battery manufacturing infra-
structure will support the engineering
of competitive mass-production pro-
cesses, many observers worry that such
support may be putting the cart before
the horse, since Li-ion battery chemis-
tries are not yet fully optimized. Others
question the government’s ability to
spend these vast sums of money effi-
ciently and effectively in the short term.
Meanwhile, researchers worldwide
continue to pursue other, potentially
more powerful chemistries for vehicular
batteries. “We’re currently looking at
Li-metal), sodium-metal-chloride, and
Li-air, all of which have safety issues,”
said the DOE’s Howell. The last system
on the list—Li-air batteries—is in fact
considered by experts to be the Holy
Grail of lithium cell technology because
the cathode would obtain its electronic
charges “for free” from atmospheric
oxygen molecules that are stripped of
electrons by a catalyst, he noted.
Current catalysts are, however, too costly
and operate at low efficiencies. In addi-
tion, said Howell, “lithium is a terrific
anode material, but the very difficult
challenge is controlling the formation of
lithium metal dendrites, tree-like struc-
tures that short out the system.”
It is unclear whether this exploratory
research on novel battery chemistries
will bear fruit, but as sales of electric-
drive vehicles rise, greater effort to de-
velop better ways to power them will
surely come as well. aei
aei JULY 2009 31