
Cylindrical 18650-cell before
closing
Lithium-ion batteries (sometimes abbreviated
Li-ion batteries) are a type of
rechargeable battery in which the
anode (positive
electrode) contains
lithium, and the
cathode
(negative electrode)is made of a type of porous
carbon. During normal operation, the
current flows (when the external circuit
is connected) from the anode to the cathode, as in any type of
battery. During this process, the battery is discharged and the
internal process occurring within the battery is the movement of
Li+ ions through the non-
aqueous
electrolyte and separator diaphragm to
the carbon cathode. The lithium ions become deeply embedded in the
carbon cathode in a process known as
intercalation. During charging,
the current is passed in the reverse direction from an external
charging circuit, the positive terminal from the charging circuit
has to be connected to the cathode of the Li-battery, and the anode
has to be connected to the negative terminal of the external
circuit. The current passed to charge the battery back up to 3.7
volts (about 4.2 volts is applied in this manner to take into
account certain factors like
internal resistance of battery etc.).
During the battery recharge process the internal change taking
place is the reverse, that is, the lithium ions present in the
carbon cathode come out , enter the electrolyte, and travel through
the electrolyte and diaphragm and get back to adhere to the anode
made of lithium metal. The electrolyte is of such nature that it
complexes with the lithium
ions, normally
manganese or
cobalt salts, are
used in the non-aqueous electrolyte for this purpose, and these
have been patented in several modifications.
Pure lithium, like
sodium, is very
reactive. It will vigorously react
with water to form lithium hydroxide and hydrogen gas is liberated.
Thus a non-aqueous electrolyte is used, and water is rigidly
excluded from the battery pack by using a sealed container.
Lithium-ion batteries are common in portable
consumer electronics because of their
high
energy-to-weight ratio, lack of
memory effect, and slow
self-discharge when not in use. In addition
to consumer electronics, lithium-ion batteries are increasingly
used in defense, automotive, and aerospace applications due to
their high energy density. However, certain kinds of mistreatment
may cause conventional Li-ion batteries to
explode.
The three primary functional components of a lithium-ion battery
are the
anode,
cathode,
and
electrolyte, for which a variety of
materials may be used. Commercially, the most popular material for
the anode is
graphite. The cathode is
generally one of three materials: a layered
oxide (such as
lithium
cobalt oxide), one based on a
polyanion (such as
lithium iron phosphate), or a
spinel (such as
lithium manganese oxide), although
materials such as TiS
2 (
titanium disulfide) originally were also
used. Depending on the choice of material for the anode, cathode,
and electrolyte, the voltage, capacity, life, and safety of a
lithium-ion battery can change dramatically. Recently,
novel
architectures have been employed to improve the performance of
these batteries. Lithium-ion batteries are not to be confused with
lithium batteries, the key
difference being that lithium batteries are
primary batteries, containing metallic
lithium, while lithium-ion batteries are
secondary batteries, containing an
intercalation anode
material.
History
Lithium-ion batteries were first proposed by
M.S. Whittingham (Binghamton University),
then at
Exxon, in the 1970s. Whittingham used
titanium sulfide as the cathode
and
lithium metal as the anode.
The electrochemical properties of the lithium intercalation in
graphite were first discovered in 1980 by
Rachid Yazami et al. at the
Grenoble Institute of
Technology (INPG) and
French National
Centre for Scientific Research (CNRS) in France. They showed
the reversible intercalation of lithium into graphite in a
lithium/polymer electrolyte/graphite
half
cell. Their work was published in 1982 and 1983. It covered
both the
thermodynamics (staging) and
the
kinetics (
diffusion) aspects of the lithium
intercalation into graphite together with reversibility.
Lithium batteries in which the anode is made from metallic lithium
pose severe safety issues. As a result, lithium-ion batteries were
developed in which the anode, like the cathode, is made of a
material containing lithium ions.
In 1981, Bell Labs
developed a workable graphite anode to provide an
alternative to the lithium
battery. Following groundbreaking cathode research by a
team led by
John Goodenough, the
first commercial lithium-ion battery was released by
Sony in 1991. The cells used layered oxide chemistry,
specifically
lithium cobalt
oxide. These batteries revolutionized consumer
electronics.
In 1983, Michael Thackeray, John Goodenough, and coworkers
identified manganese
spinel as a cathode
material. Spinel showed great promise, since it is a low-cost
material, has good electronic and lithium
ion conductivity, and possesses a
three-dimensional structure which gives it good structural
stability. Although pure manganese spinel fades with cycling, this
can be overcome with additional chemical modification of the
material. Manganese spinel is currently used in commercial
cells.
In 1989,
Arumugam Manthiram and John
Goodenough of the University of Texas at Austin
showed that cathodes containing polyanions, eg.
sulfates, produce higher voltage than oxides due to the inductive effect of the
polyanion.
In 1996, Akshaya Padhi, John Goodenough and coworkers identified
the
lithium iron phosphate
(LiFePO
4) and other phospho-
olivines (lithium metal phosphates with olivine
structure) as cathode materials for lithium-ion batteries.
LiFePO
4 is superior over other cathode materials in
terms of cost, safety, stability and performance, and is most
suitable for large batteries for electric automobiles and other
energy storage applications such as load saving, where safety is of
utmost importance. It is currently being used for most lithium-ion
batteries powering portable devices such as laptop computers and
power tools.
In 2002,
Yet-Ming Chiang and his group at MIT
published a paper in which they showed a dramatic
improvement in the performance of lithium batteries by boosting the
material's conductivity by doping it with aluminium, niobium and
zirconium, though at the time, the exact
mechanism causing the increase became the subject of a heated
debate.
In 2004, Chiang again increased performance by utilizing
iron-phosphate particles of less than
100 nm in diameter. This miniaturized the particle density by
almost a hundredfold, increased the surface area of the electrode
and improved the battery's capacity and performance.
Commercialization of the iron-phosphate technology led to a
competitive market and a patent infringement battle between Chiang
and Goodenough.
Electrochemistry
The three participants in the electrochemical reactions in a
lithium-ion battery are the
anode,
cathode, and
electrolyte.
Both the anode and cathode are materials into which and from which
lithium can migrate. The process of lithium moving into the anode
or cathode is referred to as
insertion (or
intercalation ),
and the reverse process, in which lithium moves out of the anode or
cathode is referred to as
extraction (or
deintercalation). When a lithium-based cell is
discharging,
the lithium is extracted from the anode and inserted into the
cathode. When the cell is
charging,
the reverse process occurs: lithium is extracted from the cathode
and inserted into the anode.
During discharge, the anode of a conventional Li-ion cell is made
from
carbon, the cathode is a metal
oxide, and the
electrolyte
is a
lithium salt in an
organic solvent.
Useful
work can only be extracted if
electrons flow through a (closed) external
circuit. The following equations are written in units of moles,
making it possible to use the coefficient x. The cathode
half-reaction (with charging being forwards)
is:
\mathrm{LiCoO_2} \leftrightarrows
\mathrm{Li}_{1-x}\mathrm{CoO_2} + x\mathrm{Li^+} +
x\mathrm{e^-}
The anode half reaction is:
x\mathrm{Li^+} + x\mathrm{e^-} + 6\mathrm{C}
\leftrightarrows \mathrm{Li_xC_6}
The overall reaction has its limits. Overdischarge will
supersaturate lithium cobalt oxide, leading to the production of
lithium oxide, possibly by the
following irreversible reaction:
\mathrm{Li^+} + \mathrm{LiCoO_2} \rightarrow
\mathrm{Li_2O} + \mathrm{CoO}
Overcharge up to 5.2V leads to the synthesis of cobalt(IV) oxide,
as evidenced by
x-ray diffraction
\mathrm{LiCoO_2} \rightarrow \mathrm{Li^+} +
\mathrm{CoO_2}
In a lithium-ion battery the lithium ions are transported to and
from the cathode or anode, with the transition metal,
Co, in \mathrm{Li}_x \mathrm{Co} \mathrm{O}_2 being
oxidized from Co
3+ to Co
4+ during charging,
and reduced from Co
4+ to Co
3+ during
discharge.
Cathodes
| Cathode Material |
Average Voltage |
Gravimetric Capacity |
Gravimetric Energy |
| LiCoO2 |
3.7 V |
140 mAh/g |
0.518 kW·h/kg |
| LiMn2O4 |
4.0 V |
100 mAh/g |
0.400 kW·h/kg |
| LiNiO2 |
? V |
? mAh/g |
? kW·h/kg |
| LiFePO4 |
3.3 V |
150 mAh/g |
0.495 kW·h/kg |
| Li2FePO4F |
3.6 V |
115 mAh/g |
0.414 kW·h/kg |
|
LiCo1/3Ni1/3Mn1/3O2 |
? V |
? mAh/g |
? kW·h/kg |
Anodes
| Anode Material |
Average Voltage |
Gravimetric Capacity |
Gravimetric Energy |
| Graphite (LiC6) |
0.1-0.2 V |
372 mAh/g |
0.0372-0.0744 kW·h/kg |
| Hard Carbon (LiC6) |
? V |
? mAh/g |
? kW·h/kg |
| Titanate (Li4Ti5O12) |
1-2 V |
160 mAh/g |
0.16-0.32 kW·h/kg |
| Silicium (Li22Si6) |
? V |
? mAh/g |
? kW·h/kg |
| Si (Li4.4Si) |
0.5-1 V |
4212 mAh/g |
2.106-4.212 kW·h/kg |
| Ge (Li4.4Ge) |
0.7-1.2 V |
1624 mAh/g |
1.137-1.949 kW·h/kg |
See
uranium trioxide for some
details of how the cathode works. While uranium oxides are not used
in commercially-made batteries, intercalation and deintercalation
function in the same way as with lithium-based cells.
Electrolytes
The cell voltages given in the section above are larger than the
potential at which
aqueous
solutions would
electrolyze.
Therefore, nonaqueous solutions are used.
Liquid electrolytes in lithium-ion batteries consist of
lithium salts, such as
LiPF6,
LiBF4 or
LiClO4 in an
organic solvent,
such as
ethylene carbonate. A
liquid
electrolyte conducts lithium
ions, acting as a carrier between the
cathode and the
anode when a
battery passes an electric current through an external circuit.
Typical conductivities of liquid electrolyte at room temperature
(20
oC) are in the range of 10 mS/cm, increasing by
approximately 30-40% at 40
oC and decreasing by a
slightly smaller amount at 0
oC.
Unfortunately, organic solvents are easily decomposed on
anodes during charging. However, when appropriate
organic solvents are used as the
electrolyte, the solvent is decomposed on initial charging and
forms a solid layer called the solid electrolyte interphase (SEI),
which is electrically insulating yet sufficiently conductive to
lithium ions. The interphase prevents decomposition of the
electrolyte after the second charge. For example,
ethylene carbonate is decomposed at a
relatively high voltage, 0.7 V vs. Li, and forms a dense and stable
interface.
Advantages and disadvantages
Advantages
- Lithium-ion batteries do not suffer from the memory effect. They also have a self-discharge rate of approximately 5-10%
per month, compared with over 30% per month in common nickel metal
hydride batteries, approx. 1.25% per month for Low Self-Discharge NiMH
batteries and 10% per month in nickel-cadmium batteries. According
to one manufacturer, Li-ion cells (and, accordingly, "dumb" Li-ion
batteries) do not have any self-discharge in the usual meaning of this
word. What looks like a self-discharge in these batteries is a
permanent loss of capacity (see below). On the other hand, "smart"
Li-ion batteries do self-discharge, mainly due to the small
constant drain of the built-in voltage monitoring circuit.
Disadvantages of traditional Li-ion technology
Shelf life
- A disadvantage of lithium-ion cells lies in their relatively
poor cycle life: upon every (re)charge, deposits
form inside the electrolyte that inhibit lithium ion transport,
resulting in the capacity of the cell to diminish. The increase in
internal resistance affects the cell's ability to deliver current,
thus the problem is more pronounced in high-current than
low-current applications. The increasing capacity hit means that a
full charge in an older battery will not last as long as one in a
new battery (although the charging time required decreases
proportionally, as well).
- Also, high charge levels and elevated temperatures (whether
resulting from charging or being ambient) hasten permanent capacity
loss for lithium-ion batteries. The heat generated during a charge
cycle is caused by the traditional carbon anode, which has been
replaced with good results by lithium titanate. Lithium titanate
has been experimentally shown to drastically reduce the
degenerative effects associated with charging, including expansion
and other factors. See "Improvements of lithium-ion technology"
below.
- At a 100% charge level, a typical Li-ion laptop battery that is full most of the time at 25 °C
or 77 °F will irreversibly lose approximately 20% capacity per
year. However, a battery in a poorly ventilated laptop may be
subject to a prolonged exposure to much higher temperatures, which
will significantly shorten its life. Different storage temperatures
produce different loss results: 6% loss at 0 °C (32 °F), 20% at 25
°C (77 °F), and 35% at 40 °C (104 °F). When stored at 40%–60%
charge level, the capacity loss is reduced to 2%, 4%, 15% at 0, 25
and 40 degrees Celsius respectively.
Internal resistance
The
internal resistance of
lithium-ion batteries is high compared to other rechargeable
chemistries such as
nickel-metal hydride and
nickel-cadmium. It increases
with both cycling and chronological age. Rising internal resistance
causes the voltage at the terminals to drop under load, reducing
the maximum current that can be drawn from them. Eventually they
reach a point at which the battery can no longer operate the
equipment it is installed in for an adequate period.
High drain applications such as power tools may require the battery
to be able to supply a current that would drain the battery in 1/15
hour if sustained; e.g. 22.5 A for a battery with a capacity
of 1.5
A·h). Lower-power devices
such as
MP3 players, on the other hand,
may draw low enough current to run for 10 hours on a charge (e.g.
150 mA for a battery with a capacity of 1500 mA·h). With
similar battery technology, the MP3 player's battery will
effectively last much longer, since it can tolerate a much higher
internal resistance. To power larger devices, such as electric
cars, it is much more efficient to connect many smaller batteries
in a parallel circuit rather than using a single large
battery.
Safety requirements
Li-ion batteries are not as durable as
nickel metal hydride or
nickel-cadmium designs, and
can be extremely dangerous if mistreated. They may explode if
overheated or if charged to an excessively high voltage.
Furthermore, they may be irreversibly damaged if discharged
below a certain voltage. To reduce these risks,
lithium-ion batteries generally contain a small circuit that shuts
down the battery when it is discharged below about 3 V or
charged above about 4.2 V. In normal use, the battery is
therefore prevented from being deeply discharged. When stored for
long periods, however, the small current drawn by the protection
circuitry may drain the battery below the protection circuit's
lower limit, in which case normal chargers are unable to recharge
the battery. More sophisticated battery analyzers can recharge
deeply discharged cells by slow-charging them .
Other safety features are also required for commercial lithium-ion
batteries:
- shut-down separator (for overtemperature),
- tear-away tab (for internal pressure),
- vent (pressure relief), and
- thermal interrupt (overcurrent/overcharging).
These devices occupy useful space inside the cells, and reduce
their reliability ; typically, they permanently and irreversibly
disable the cell when activated. They are required because the
anode produces heat during use, while the cathode may produce
oxygen. Safety devices and recent and improved electrode designs
greatly reduce or eliminate the risk of fire or explosion.
These safety features increase the cost of lithium-ion batteries
compared to nickel metal hydride cells, which only require a
hydrogen/oxygen recombination device (preventing damage due to mild
overcharging) and a back-up pressure valve.
Many types of lithium-ion cell cannot be charged safely below 0
°C.
Product recalls
About 1% of lithium-ion batteries are recalled.
Specifications and design

A lithium-ion battery from a mobile
phone.
- Specific energy density: 150 to 200 Wh/kg (540 to 720 kJ/kg)
- Volumetric energy density: 250 to 530 Wh/l (900 to 1900
J/cm³)
- Specific power density: 300 to 1500 W/kg (@ 20 seconds and 285
Wh/l)
Because lithium-ion batteries can have a variety of cathode and
anode materials, the energy density and voltage vary
accordingly.
Lithium-ion batteries with a lithium iron phosphate cathode and
graphite anode have a nominal
open-circuit voltage of 3.2
V and a typical charging voltage of 3.6 V. Lithium
nickel manganese cobalt (NMC) oxide cathode with graphite anodes
have a 3.7 V nominal voltage with a 4.2 V max charge. The charging
procedure is performed at constant voltage with current-limiting
circuitry (i.e., charging with constant current until a voltage of
4.2 V is reached in the cell and continuing with a constant voltage
applied until the current drops close to zero). Typically, the
charge is terminated at 7% of the initial charge current. In the
past, lithium-ion batteries could not be fast-charged and typically
needed at least two hours to fully charge. Current-generation cells
can be fully charged in 45 minutes or less; some lithium-ion
varieties can reach 90% in as little as 10 minutes.
Charging procedure
Stage 1: Apply charging current limit until the
voltage limit per cell is reached.
Stage 2: Apply maximum voltage per cell limit
until the current declines below 3% of rated charge current.
Stage 3: Periodically apply a top-off charge about
once per 500 hours.
The charge time is about three to five hours, depending upon the
charger used. Generally, cell phone batteries can be charged at 1C
and laptop-types at 0.8C, where C is the current that would
discharge the battery in one hour. Charging is usually stopped when
the current goes below 0.03C but it can be left indefinitely
depending on desired charging time. Some fast chargers skip stage 2
and claim the battery is ready at 70% charge.Laptop battery
chargers sometimes gamble, and try to charge up to 4.35v then
disconnect battery. This helps to compensate internal resistance
and charge up to 100% in short time.
Top-off charging is recommended to be initiated when voltage goes
below 4.05 V/cell.
Lithium-ion cells are charged with
4.2 ± 0.05 V/cell,except for military long-life
cells where 3.92 V is used to extend battery life. Most
protection circuits cut off if either 4.3 V or 90 °C is
reached. If the voltage drops below 2.50 V per cell, the
battery protection circuit may also render it unchargeable with
regular charging equipment. Most battery protection circuits stop
at 2.7–3.0 V per cell.
For safety reasons it is recommended to stay within the
manufacturer's stated voltage and current ratings during both
charge and discharge cycles.
Technology improvements
Overview
Improvements focus on several areas, and often involve advances in
nanotechnology and microstructures.
- Increasing cycle life and performance (decreases internal
resistance and increases output power) by changing the composition
of the material used in the anode and cathode, along with
increasing the effective surface area of the electrodes (related
developments have helped ultracapacitors) and changing materials used
in the electrolyte and/or combinations thereof (e.g., Li-VOx-based
cells with polymer electrolyte).
- Improving capacity by improving the structure to incorporate
more active materials.
- Improving the safety of lithium-ion batteries.
Manganese spinel cathodes
LG (Lucky Goldstar Chemical), which is the
third-largest producer of lithium-ion batteries, uses the lithium
manganese spinel for its cathode.
It is working with its subsidiary
CPI to
commercialize lithium-ion batteries containing manganese
spinel for
HEV
applications. Several other companies are also working with
manganese spinel, including
NEC and
Samsung.
Lithium iron phosphate cathode with traditional anode
The
University of
Texas
first licensed its patent for lithium iron
phosphate cathodes to the Canadian
utility Hydro-Québec. Phostech Lithium inc. was later
spun-off from Hydro-Québec for the sole development of lithium iron
phosphate.
Valence Technology, located in
Austin, Texas, is also working on lithium iron magnesium phosphate
cells. Since March 2005, the
Segway Personal Transporter has
been shipping with extended-range lithium-ion batteries made by
Valence Technology using iron magnesium phosphate cathode
materials. Segway, Inc. chose to build their large-format battery
with this cathode material because of its improved safety over
metal-oxide materials. To date Valence has shipped 100,000
batteries to Segway.
In November 2005,
A123Systems announced
the development of lithium iron phosphate cells based on research
licensed from MIT. While the battery has slightly lower energy
density than other competing lithium-ion technologies, a 2 Ah cell
can provide a peak of 70 Amps without damage and operate at
temperatures above 60 degrees C. Their first cell has been in
production since 2006 and is being used in consumer products
including
DeWalt power tools, aviation
products, automotive hybrid systems and
PHEV
conversions.
LiFePO
4 cells are currently available
commercially.
High power cathode using lithium nickel manganese cobalt
(NMC)
Imara Corporation, based in Menlo
Park, CA is commercializing a new
materials-agnostic
technology first applied on an NMC material which has the effect of
lowering impedance and extending cycle life. These high
power-capable cells have high energy density relative to other high
power cells in the market. The batteries are being deployed in
power tools, outdoor power equipment and hybrid vehicles; Sony and
Sanyo use NMC and NCA blended with LMO (spinel) for high-powered
applications. NMC has a significant safety advantage over cobalt
oxide and 50% greater energy density than FePO4, but suffers from a
poor cycle life.
Traditional cathode with lithium titanate anode
Altairnano, a small firm based in Reno, Nevada
, has announced a nano-sized titanate electrode
material for lithium-ion batteries. It is claimed the
prototype battery has three times the power output of existing
batteries and can be fully charged in six minutes. However, total
energy capacity per cell is about half that of normal lithium-ion
cells. The company also says the battery cells have now achieved a
life of over 9,000 charge cycles while still retaining up to 85%
charge capacity. Durability and battery life are therefore much
longer, estimated to be around 20 years, or four times longer than
regular lithium-ion batteries. The batteries can operate from -50
°C to over 75 °C and will not explode or experience thermal
runaway, even under severe conditions, because they do not contain
graphite-coated-metal anode electrode material. The batteries are
currently being tested in a new production car made by
Phoenix Motorcars which was on display at
the 2006 SEMA motorshow.
They're also being tested, on a one MW grid scale, in the PJM Interconnection Regional
Transmission Organization control area in Norristown,
Pennsylvania
as well as by several branches of the United States
Department of Defense
. In addition, the batteries are being
demonstrated by Proterra in their all-electric EcoRide BE35
vehicle, a lightweight 35-foot bus. Altairnano is currently working
with three different cell chemistries for various energy and power
storage applications, with another new cell chemistry expected in
the fall of 2009. The nature of their latest cathode materials is
currently proprietary.
Combined anode and cathode developments
EnerDel, which is jointly owned by
Ener1 and
Delphi, is
working to commercialize cells containing a
titanate anode and
manganese spinel cathode.
Although the cells show excellent thermal properties and
cyclability, their low voltage may hamper
commercial success.
Research claims
In April 2006, a group of scientists at MIT announced a process
which uses
viruses to form nano-sized wires.
These can be used to build ultrathin lithium-ion batteries with
three times the normal energy density.
As of June 2006, researchers in France have created
nanostructured
battery electrodes with several times the energy capacity, by
weight and volume, of conventional electrodes.
In the September 2007 issue of
Nature, researchers from
the University of Waterloo, Canada, reported a new cathode
chemistry, in which the hydroxyl group in the iron phosphate
cathode was replaced by fluorine. The advantages seem to be
two-fold. First, there is less volume change in the cathode over a
charge cycle which may improve battery life. Secondly, the
chemistry allows the substitution of the lithium in the battery
with either sodium or a sodium/lithium mixture (hence their
reference to it as an
Alkali-Ion
battery).
In November 2007,
Subaru unveiled their
concept G4e electric vehicle with a lithium
vanadium oxide-based lithium-ion battery, promising
double the energy density of a conventional lithium-ion battery
(lithium cobalt oxide and graphite). In the lab, lithium vanadium
oxide anodes, paired with lithium cobalt oxide cathodes, have
achieved 745Wh/l, nearly three times the volumetric energy density
of conventional lithium-ion batteries.
In December 2007, researchers at Stanford University reported
creating a lithium-ion
nanowire
battery with ten times the energy density (amount of energy
available by weight) through using silicon nanowires deposited on
stainless steel as the anode. The battery takes advantage of the
fact that silicon can hold large amounts of lithium, and helps
alleviate the longstanding problem of cracking by the small size of
the wires. To gain a tenfold improvement in energy density, the
cathode would need to be improved as well; however, even just
improving the anode could provide "several" times the energy
density, according to the team. The team leader, Yi Cui, expects to
be able to commercialize the technology in about five years. Having
a large capacitive anode will not increase the capacity of the
battery as predicted by the author when the cathode material is far
less capacitive than the anode. However, current lithium-ion
capacity is mainly limited by the low theoretical capacity (372 mAh
g
−1) of the graphite in use as the anode material, so
improvement could be significant and would then be limited by the
cathode material instead.
There are trials with metal
hydrides as
anode material for lithium-ion batteries. A practical electrode
capacity as high as 1480 mAh g
−1 has been
reported.
In April 2009 a report in
New
Scientist claimed that Angela Belcher's team at MIT had
succeeded in producing the first full virus-based 3-volt
lithium-ion battery.
In November 2009, engineers at the
University of Dayton
Research Institute developed the world's first solid-state,
rechargeable lithium air battery which was designed
to address the
fire and
explosion risk of other lithium rechargeable
batteries and make way for development of large-size lithium
rechargeables for a number of industry applications, including
hybrid and
electric
cars.
Recent
studies performed at Binghamton University
by M. S. Whittingham et al. determined that
vanadium ions can be incorporated into the iron-containing olivine
structure of LiFePO4; a small amount of vanadium (around 5%)
enhancing the rate capability of the LiFePO4 olivine cathode
material. The resulting compound material had higher electronic and
ionic conductivities, and they were of comparable magnitude. The
doping reaction kinetics were optimal under reducing atmosphere
during the synthesis of the LiFe0.95V0.05PO4 material.
Guidelines for prolonging lithium-ion battery life
- Lithium-ion batteries should never be depleted below their minimum voltage (2.4 to
2.8 V/cell, depending on chemistry). If a lithium-ion battery is
stored with too low a charge, there is a risk that the charge will
drop below the low-voltage threshold, resulting in an unrecoverable
dead battery. Usually this does not instantly damage the battery
itself but a charger or device which uses that battery will refuse
to charge a dead battery. The battery appears to be dead or not
existent because the protection circuit disables further
discharging and there is zero voltage on the battery
terminals.
- Lithium-ion batteries should be kept cool. Ideally they are
stored in a refrigerator.
- Aging will take its toll much faster at high temperatures.
Prolonging life in multiple cells through cell balancing
Analog front ends that balance cells and eliminate mismatches of
cells in series or parallel significantly improve battery
efficiency and increase the overall pack capacity. As the number of
cells and load currents increase, the potential for mismatch also
increases. There are two kinds of mismatch in the pack:
state-of-charge (SOC) and capacity/energy (C/E) mismatch. Though
the SOC mismatch is more common, each problem limits the pack
capacity (mAh) to the capacity of the weakest cell.
Safety
Lithium-ion batteries can rupture, ignite, or explode when exposed
to high-temperature environments, e.g. in an area that is prone to
prolonged direct sunlight.
Short-circuiting a lithium-ion battery can
cause it to ignite or explode and any attempt to open or modify the
casing or circuitry is dangerous. For this reason they normally
contain safety devices that protect the cells from abuse.
Contaminants inside the cells can defeat these safety devices.
For
example, the mid-2006 recall of approximately 10 million Sony
batteries used in Dell, Sony, Apple
, Lenovo/IBM, Panasonic, Toshiba,
Hitachi, Fujitsu and Sharp
laptops was stated to be as a consequence of internal contamination
with metal particles. Under some circumstances, these can
pierce the separator, causing the cell to short, rapidly converting
all of the energy in the cell to heat resulting in an
exothermic oxidizing reaction, increasing the
temperature to a few hundred degrees Celsius in a fraction of a
second. This causes the neighboring cells to heat up, causing a
chain reaction.
The mid-2006 Sony laptop battery recall was not the first of its
kind; it was, however, the largest to date. During the past decade,
there have been numerous recalls of lithium-ion batteries in
cellular phones and laptops owing to overheating problems. In
October 2004,
Kyocera Wireless
recalled approximately 1 million batteries used in cellular phones
due to
counterfeit batteries produced in
Kyocera's name. In December 2006,
Dell recalled
approximately 22,000 batteries from the U.S. market. In March 2007,
Lenovo recalled approximately 205,000 9-cell lithium-ion batteries
due to an explosion risk. In August 2007,
Nokia recalled over 46 million lithium-ion batteries,
warning that some of them might overheat and possibly explode.
One such
incident occurred in the Philippines
involving an Nokia N91,
which uses the BL-5C battery.
Replacing the
lithium cobalt
oxide cathode material in lithium-ion batteries with
lithiated metal phosphate leads to
longer cycle and shelf life, improves safety, but lowers capacity.
Currently these 'safer' lithium-ion batteries are mainly used in
electric cars and other
large-capacity battery applications,
where safety issues are critical.
Another option is to use a
manganese
oxide or
iron phosphate
cathode.
A new class of high power cathode materials, lithium nickel
manganese cobalt (NMC) oxide has recently been introduced that have
a significantly higher temperature tolerance compared to lithium
cobalt oxide (see above).
In the event of a lithium-ion battery explosion, dense white smoke
which can cause severe irritation to the respiratory tract, eyes
and skin will be generated. All precautions must be taken to limit
exposure to these fumes.
Restrictions on transportation
As of January 2008, the
United States
Department of Transportation issued a new rule that permits
passengers on board commercial aircraft to carry lithium batteries
in their checked baggage IF the batteries are installed in a
device. Types of batteries affected by this rule are those
containing lithium, including Li-ion,
lithium polymer, and
lithium cobalt oxide chemistries.
Lithium-ion batteries containing more than 25 grams Equivalent
Lithium Content (ELC) are exempt from the rule and are forbidden in
air travel.
The purpose of this restriction is that it greatly reduces the
chances of the batteries becoming short-circuited and causing a
fire. A limited number of replacement batteries can be carried in
hand luggage providing they are kept in their original protective
packaging or in individual containers or plastic bags.
See also
References
- MRS Website : Theme Article - Science and
Applications of Mixed Conductors for Lithium Batteries
- Electrical Energy Storage and Intercalation
Chemistry - WHITTINGHAM 192 (4244): 1126 - Science
- Yazami, R. and Touzain, Ph., International Meeting on
Lithium Batteries, Rome, April 27–29, 1982, C.L.U.P. Ed.
Milan, Abstract # 23
- USPTO search for inventions by "Goodenough,
John"
- IEEE Spectrum: Lithium Batteries Take to the Road
- Silberberg, M. 2006. Chemistry: The Molecular Nature of
Matter and Change, 4th Ed. New York (NY): McGraw-Hill
Education. p 935.
- H.C. Choi et al., J. Phys. Chem. B 107 p5806(2003)
doi:10.1021/jp030438w
- G.G. Amatucci, J.M. Tarascon, L.C. Kein J. Electrochemical
Society 143 p1114 1996 doi:10.1149/1.1836594
- Elektor Magazine, september 2009
- http://www.cheric.org/PDF/Symposium/S-J2-0063.pdf
- Balbuena, P.B., Wang, Y.X., eds. Lithium Ion Batteries:
Solid Electrolyte Interphase 2004 Imperial College Press,
London
- M. Winter and J. Brodd, Chem. Rev. 104 (2004), pp. 4256 (for
comparison to alkaline cells) and 4258 (for comparison to Ni-MH
cells)
- M. Winter and J. Brodd, Chem. Rev. 104 (2004), pp. 4254
- M. Winter and J. Brodd, Chem. Rev. 104 (2004), pp. 4259 ad
4.
- Aging - capacity loss
- M. Winter and J. Brodd, Chem. Rev. 104 (2004), pp. 4258
- Altair Nano: Power & Energy Systems
- Battery University: Fig. 1 Non-recoverable capacity
loss
- M. Winter and J. Brodd, Chem. Rev. 104 (2004), pp. 4259
- Electronic Letter Format
- AeroVironment Achieves Electric Vehicle Fast Charge
Milestone Test Rapidly Recharges a Battery Pack Designed for
Use in Passenger Vehicles. 10 Minute Re-Charge Restores Enough
Energy to Run Electric Vehicle for Two Hours at 60 Miles Per
Hour
-
http://www.aei-online.org/automag/techbriefs/10-2006/1-114-10-16.pdf
- IEEE Spectrum: Lithium Batteries Take to the Road
- Bickel & Brewer - A law firm devoted
exclusively to the resolution of complex commercial
disputes.
- Segway | Products | Segway HT | Lithium-Ion
Batteries
- Missing View
- Green Car Congress: A123Systems Launches New
Higher-Power, Faster Recharging Li-Ion Battery Systems
- Yahoo! Groups
- Imara
- Microsoft PowerPoint - 061125 Altair EDTA
Presentation
- Altair Nanotechnologies Power Partner - The
Military
- Welcome to Ener1
- Microsoft PowerPoint - EnerDel Technical Presentation.ppt
[Read-Only]
- Science Express (preprint)
http://www.sciencemag.org/cgi/content/abstract/1122716
- Technology Review: Higher-Capacity Lithium-Ion
Batteries
- Redirect Notice
-
http://web.archive.org/web/20080414071653/http://www.tayloredge.com/museum/mymuseum/sciencefun/li-ion_003.mov
- Dell laptop explodes at Japanese conference - The
INQUIRER
- Tullo, Alex. "Dell Recalls Lithium Batteries." Chemical and
Engineering News 21 August 2006: 11.
- Nokia N91 cell phone explodes
- Safety Last - New York Times
- Technology Review: New Batteries Readied for GM's Electric
Vehicle
- 2009-05-21 marine.rutgers.edu
External links