Is Lithium-ion the Ideal Battery?

For many years, nickel-cadmium had been the only suitable battery for portable equipment from
wireless communications to mobile computing. Nickel-metal-hydride and lithium-ion emerged In the
early 1990s, fighting nose-to-nose to gain customer's acceptance. Today, lithium-ion is the fastest
growing and most promising battery chemistry.

The lithium-ion battery

Pioneer work with the lithium battery began in 1912 under G.N. Lewis but it was not until the early 1970s
when the first non-rechargeable lithium batteries became commercially available. lithium is the lightest
of all metals, has the greatest electrochemical potential and provides the largest energy density for
weight.

Attempts to develop rechargeable lithium batteries failed due to safety problems. Because of the
inherent instability of lithium metal, especially during charging, research shifted to a non-metallic lithium
battery using lithium ions. Although slightly lower in energy density than lithium metal, lithium-ion is safe,
provided certain precautions are met when charging and discharging

The energy density of lithium-ion is typically twice that of the standard nickel-cadmium. There is
potential for higher energy densities. The load characteristics are reasonably good and behave similarly
to nickel-cadmium in terms of discharge. The high cell voltage of 3.6 volts allows battery pack designs
with only one cell. Most of today's mobile phones run on a single cell. A nickel-based pack would require
three 1.2-volt cells connected in series.

Lithium-ion is a low maintenance battery, an advantage that most other chemistries cannot claim. There
is no memory and no scheduled cycling is required to prolong the battery's life. In addition, the self-
discharge is less than half compared to nickel-cadmium, making lithium-ion well suited for modern fuel
gauge applications. lithium-ion cells cause little harm when disposed.

Despite its overall advantages, lithium-ion has its drawbacks. It is fragile and requires a protection
circuit to maintain safe operation. Built into each pack, the protection circuit limits the peak voltage of
each cell during charge and prevents the cell voltage from dropping too low on discharge. In addition,
the cell temperature is monitored to prevent temperature extremes. The maximum charge and discharge
current on most packs are is limited to between 1C and 2C. With these precautions in place, the
possibility of metallic lithium plating occurring due to overcharge is virtually eliminated.

Aging is a concern with most lithium-ion batteries and many manufacturers remain silent about this
issue. Some capacity deterioration is noticeable after one year, whether the battery is in use or not. The
battery frequently fails after two or three years. It should be noted that other chemistries also have age-
related degenerative effects. This is especially true for nickel-metal-hydride if exposed to high ambient
temperatures. At the same time, lithium-ion packs are known to have served for five years in some
applications.
 Manufacturers are constantly improving lithium-ion. New and enhanced chemical combinations are
introduced every six months or so. With such rapid progress, it is difficult to assess how well the revised
battery will age.

Storage in a cool place slows the aging process of lithium-ion (and other chemistries). Manufacturers
recommend storage temperatures of 15°C (59°F). In addition, the battery should be partially charged
during storage. The manufacturer recommends a 40% charge.

The most economical lithium-ion battery in terms of cost-to-energy ratio is the cylindrical 18650 (size is
18mm x 65.2mm). This cell is used for mobile computing and other applications that do not demand
ultra-thin geometry. If a slim pack is required, the prismatic lithium-ion cell is the best choice. These cells
come at a higher cost in terms of stored energy.

Advantages

1 High energy density - potential for yet higher capacities.

2 Does not need prolonged priming when new. One regular charge is all that's needed.

3 Relatively low self-discharge - self-discharge is less than half that of nickel-based batteries.

4 Low Maintenance - no periodic discharge is needed; there is no memory.

5 Specialty cells can provide very high current to applications such as power tools.

Limitations

6 Requires protection circuit to maintain voltage and current within safe limits.

7 Subject to aging, even if not in use - storage in a cool place at 40% charge reduces the aging

effect.

8 Transportation restrictions - shipment of larger quantities may be subject to regulatory control.

This restriction does not apply to personal carry-on batteries.

 9 Expensive to manufacture - about 40 percent higher in cost than nickel-cadmium.

10 Not fully mature - metals and chemicals are changing on a continuing basis.

The lithium polymer battery

The lithium-polymer differentiates itself from conventional battery systems in the type of electrolyte used.
The original design, dating back to the 1970s, uses a dry solid polymer electrolyte. This electrolyte
resembles a plastic-like film that does not conduct electricity but allows ions exchange (electrically
charged atoms or groups of atoms). The polymer electrolyte replaces the traditional porous separator,
which is soaked with electrolyte.

The dry polymer design offers simplifications with respect to fabrication, ruggedness, safety and thin-
profile geometry. With a cell thickness measuring as little as one millimeter (0.039 inches), equipment
designers are left to their own imagination in terms of form, shape and size.

Unfortunately, the dry lithium-polymer suffers from poor conductivity. The internal resistance is too high
and cannot deliver the current bursts needed to power modern communication devices and spin up the
hard drives of mobile computing equipment. Heating the cell to 60°C (140°F) and higher increases the
conductivity, a requirement that is unsuitable for portable applications.

To compromise, some gelled electrolyte has been added. The commercial cells use a separator/
electrolyte membrane prepared from the same traditional porous polyethylene or polypropylene
separator filled with a polymer, which gels upon filling with the liquid electrolyte. Thus the commercial
lithium-ion polymer cells are very similar in chemistry and materials to their liquid electrolyte counter
parts.

Lithium-ion-polymer has not caught on as quickly as some analysts had expected. Its superiority to
other systems and low manufacturing costs has not been realized. No improvements in capacity gains
are achieved - in fact, the capacity is slightly less than that of the standard lithium-ion battery. Lithium-
ion-polymer finds its market niche in wafer-thin geometries, such as batteries for credit cards and other
such applications.

Advantages

11 Very low profile - batteries resembling the profile of a credit card are feasible.

12 Flexible form factor - manufacturers are not bound by standard cell formats. With high volume,
any reasonable size can be produced economically.

13 Lightweight - gelled electrolytes enable simplified packaging by eliminating the metal shell.
 14 Improved safety - more resistant to overcharge; less chance for electrolyte leakage.

Limitations

15 Lower energy density and decreased cycle count compared to lithium-ion.

16 Expensive to manufacture.

17 No standard sizes. Most cells are produced for high volume consumer markets.

18 Higher cost-to-energy ratio than lithium-ion

Restrictions on lithium content for air travel

Air travelers ask the question, "How much lithium in a battery am I allowed to bring on board?" We
differentiate between two battery types: Lithium metal and lithium-ion.
Most lithium metal batteries are non-rechargeable and are used in film cameras. Lithium-ion packs are
rechargeable and power laptops, cellular phones and camcorders. Both battery types, including spare
packs, are allowed as carry-on but cannot exceed the following lithium content:
- 2 grams for lithium metal or lithium alloy batteries
- 8 grams for lithium-ion batteries

Lithium-ion batteries exceeding 8 grams but no more than 25 grams may be carried in carry-on baggage
if individually protected to prevent short circuits and are limited to two spare batteries per person.

How do I know the lithium content of a lithium-ion battery? From a theoretical perspective, there is
no metallic lithium in a typical lithium-ion battery. There is, however, equivalent lithium content that must
be considered. For a lithium-ion cell, this is calculated at 0.3 times the rated capacity (in ampere-hours).

Example: A 2Ah 18650 Li-ion cell has 0.6 grams of lithium content. On a typical 60 Wh laptop battery
with 8 cells (4 in series and 2 in parallel), this adds up to 4.8g. To stay under the 8-gram UN limit, the
largest battery you can bring is 96 Wh. This pack could include 2.2Ah cells in a 12 cells arrangement
(4s3p). If the 2.4Ah cell were used instead, the pack would need to be limited to 9 cells (3s3p).

Restrictions on shipment of lithium-ion batteries

19 Anyone shipping lithium-ion batteries in bulk is responsible to

meet transportation regulations. This applies to domestic and
international shipments by land, sea and air.

20 Lithium-ion cells whose equivalent lithium content exceeds 1.5

grams or 8 grams per battery pack must be shipped as "Class 9
 miscellaneous hazardous material." Cell capacity and the number
of cells in a pack determine the lithium content.

21 Exception is given to packs that contain less than 8 grams of

lithium content. If, however, a shipment contains more than 24
lithium cells or 12 lithium-ion battery packs, special markings and
shipping documents will be required. Each package must be
marked that it contains lithium batteries.

22 All lithium-ion batteries must be tested in accordance with

specifications detailed in UN 3090 regardless of lithium content
(UN manual of Tests and Criteria, Part III, subsection 38.3). This
precaution safeguards against the shipment of flawed batteries.

23 Cells & batteries must be separated to prevent short-circuiting

and packaged in strong boxes.

Lithium-ion batteries are popular because they have a

number of important advantages over competing

technologies:

24 They're generally much lighter than other types of

rechargeable batteries of the same size. The electrodes

of a lithium-ion battery are made of lightweight lithium

and carbon. Lithium is also a highly reactive element,

meaning that a lot of energy can be stored in its atomic

bonds. This translates into a very high energy density for

 lithium-ion batteries. Here is a way to get a perspective

on the energy density. A typical lithium-ion battery can

store 150 watt-hours of electricity in 1 kilogram of

battery. A NiMH (nickel-metal hydride) battery pack can

store perhaps 100 watt-hours per kilogram, although 60

to 70 watt-hours might be more typical. A lead-acid

battery can store only 25 watt-hours per kilogram. Using

lead-acid technology, it takes 6 kilograms to store the

same amount of energy that a 1 kilogram lithium-ion

battery can handle. That's a huge difference [s

25 ource: Everything2.com].

26 They hold their charge. A lithium-ion battery pack loses

only about 5 percent of its charge per month, compared

to a 20 percent loss per month for NiMH batteries.

27 They have no memory effect, which means that you do

not have to completely discharge them before recharging,

as with some other battery chemistries.

28 Lithium-ion batteries can handle hundreds of

charge/discharge cycles.

That is not to say that lithium-ion batteries are flawless.

They have a few disadvantages as well:

 29 They start degrading as soon as they leave the factory.

They will only last two or three years from the date of

manufacture whether you use them or not.

30 They are extremely sensitive to high temperatures.

Heat causes lithium-ion battery packs to degrade much

faster than they normally would.

31 If you completely discharge a lithium-ion battery, it is

ruined.

32 A lithium-ion battery pack must have an on-board

computer to manage the battery. This makes them even

more expensive than they already are.

33 There is a small chance that, if a lithium-ion battery

pack fails, it will burst into flame.

Many of these characteristics can be understood by looking

at the chemistry inside a lithium-ion cell. We'll look at this

next.

Lithium-ion battery packs come in all shapes and sizes, but

they all look about the same on the inside. If you were to

take apart a laptop battery pack (something that we DO NOT

recommend because of the possibility of shorting out a

battery and starting a fire) you would find the following:

 34 The lithium-ion cells can be either cylindrical batteries

that look almost identical to AA cells, or they can be

prismatic, which means they are square or rectangular

The computer, which comprises:

35 One or more temperature sensors to monitor the

battery temperature

36 A voltage converter and regulator circuit to maintain

safe levels of voltage and current

37 A shielded notebook connector that lets power and

information flow in and out of the battery pack

38 A voltage tap, which monitors the energy capacity of

individual cells in the battery pack

39 A battery charge state monitor, which is a small

computer that handles the whole charging process to

make sure the batteries charge as quickly and fully as

possible.

If the battery pack gets too hot during charging or use, the

computer will shut down the flow of power to try to cool

things down. If you leave your laptop in an extremely hot car

and try to use the laptop, this computer may prevent you

from powering up until things cool off. If the cells ever

become completely discharged, the battery pack will shut

down because the cells are ruined. It may also keep track of

the number of charge/discharge cycles and send out

information so the laptop's battery meter can tell you how

much charge is left in the battery.

Lithium-ion Cells

As with most batteries you have an outer case made of

metal. The use of metal is particularly important here

because the battery is pressurized. This metal case has

some kind of pressure-sensitive vent hole. If the battery

ever gets so hot that it risks exploding from over-pressure,

this vent will release the extra pressure. The battery will

probably be useless afterwards, so this is something to

avoid. The vent is strictly there as a safety measure. So is

the Positive Temperature Coefficient (PTC) switch, a device

that is supposed to keep the battery from overheating.

This metal case holds a long spiral comprising three thin

sheets pressed together:

40 A Positive electrode

41 A Negative electrode

42 A separator

Inside the case these sheets are submerged in an organic

solvent that acts as the electrolyte. Ether is one common

solvent.

The separator is a very thin sheet of microperforated

plastic. As the name implies, it separates the positive and

negative electrodes while allowing ions to pass through.

The positive electrode is made of Lithium cobalt oxide, or

LiCoO2. The negative electrode is made of carbon. When the

battery charges, ions of lithium move through the

electrolyte from the positive electrode to the negative

electrode and attach to the carbon. During discharge, the

lithium ions move back to the LiCoO2 from the carbon.

The movement of these lithium ions happens at a fairly high

voltage, so each cell produces 3.7 volts. This is much higher

than the 1.5 volts typical of a normal AA alkaline cell that

you buy at the supermarket and helps make lithium-ion

batteries more compact in small devices like cell phones.

See How Batteries Work for details on different battery

chemistries.

We'll look at how to prolong the life of a lithium-ion battery

and explore why they can explode next.

Lithium-ion battery packs are expensive, so if you want to

make yours to last longer, here are some things to keep in

mind:

43 Lithium ion chemistry prefers partial discharge to deep

discharge, so it's best to avoid taking the battery all the

way down to zero. Since lithium-ion chemistry does not

have a "memory", you do not harm the battery pack with

a partial discharge. If the voltage of a lithium-ion cell

drops below a certain level, it's ruined.

44 Lithium-ion batteries age. They only last two to three

years, even if they are sitting on a shelf unused. So do not

"avoid using" the battery with the thought that the

battery pack will last five years. It won't. Also, if you are

buying a new battery pack, you want to make sure it

really is new. If it has been sitting on a shelf in the store

 for a year, it won't last very long. Manufacturing dates are

important.

45 Avoid heat, which degrades the batteries.

Exploding Batteries

Now that we know how to keep lithium-ion batteries working

longer, let's look at why they can explode.

If the battery gets hot enough to ignite the electrolyte, you

are going to get a fire. There are video clips and photos on

the Web that show just how serious these fires can be. The

CBC article,"Summer of the Exploding Laptop," rounds up

several of these incidents.

When a fire like this happens, it is usually caused by an

internal short in the battery. Recall from the previous

section that lithium-ion cells contain a separator sheet that

keeps the positive and negative electrodes apart. If that

sheet gets punctured and the electrodes touch, the battery

heats up very quickly. You may have experienced the kind of

heat a battery can produce if you have ever put a normal 9-

volt battery in your pocket. If a coin shorts across the two

terminals, the battery gets quite hot.

In a separator failure, that same kind of short happens

inside the lithium-ion battery. Since lithium-ion batteries are

so energetic, they get very hot. The heat causes the battery

to vent the organic solvent used as an electrolyte, and the

heat (or a nearby spark) can light it. Once that happens

inside one of the cells, the heat of the fire cascades to the

other cells and the whole pack goes up in flames.

It is important to note that fires are very rare. Still, it only

takes a couple of fires and a little media coverage to prompt

a recall.

THE BASICS

A battery is made up of an anode, cathode, separator,

electrolyte, and two current collectors (positive and

negative). The anode and cathode store the lithium. The

electrolyte carries positively charged lithium ions from the

anode to the cathode and vice versa through the separator.

The movement of the lithium ions creates free electrons in

the anode which creates a charge at the positive current

collector. The electrical current then flows from the current

collector through a device being powered (cell phone,

computer, etc.) to the negative current collector. The

separator blocks the flow of electrons inside the battery.

CHARGE/DISCHARGE

While the battery is discharging and providing an electric

current, the anode releases lithium ions to the cathode,

generating a flow of electrons from one side to the other.

When plugging in the device, the opposite happens: Lithium

ions are released by the cathode and received by the anode.

ENERGY DENSITY VS. POWER DENSITY

The two most common concepts associated with batteries

are energy density and power density. Energy density is

measured in watt-hours per kilogram (Wh/kg) and is the

amount of energy the battery can store with respect to its

mass. Power density is measured in watts per kilogram

(W/kg) and is the amount of power that can be generated by

the battery with respect to its mass. To draw a clearer

picture, think of draining a pool. Energy density is similar to

the size of the pool, while power density is comparable to

draining the pool as quickly as possible.

The Vehicle Technologies Office works on increasing the

energy density of batteries, while reducing the cost, and

maintaining an acceptable power density. For more

information on VTO’s battery-related projects, please visit

www.vehicles.energy.gov

Like any other battery, a rechargeable lithium-ion battery is

made of one or more power-generating compartments called

cells. Each cell has essentially three components: a

positive electrode (connected to the battery's positive or

+ terminal), a negative electrode (connected to the

negative or − terminal), and a chemical called an

electrolyte in between them. The positive electrode is

typically made from a chemical compound called lithium-

cobalt oxide (LiCoO ) or, in newer batteries, from lithium iron

2

phosphate (LiFePO ). The negative electrode is generally

4

made from carbon (graphite) and the electrolyte varies from

one type of battery to another—but isn't too important in

understanding the basic idea of how the battery works.

All lithium-ion batteries work in broadly the same way. When

the battery is charging up, the lithium-cobalt oxide, positive

electrode gives up some of its lithium ions, which move

through the electrolyte to the negative, graphite electrode

and remain there. The battery takes in and stores energy

during this process. When the battery is discharging, the

lithium ions move back across the electrolyte to the positive

electrode, producing the energy that powers the battery. In

both cases, electrons flow in the opposite direction to the

ions around the outer circuit. Electrons do not flow through

the electrolyte: it's effectively an insulating barrier, so far as

electrons are concerned.

The movement of ions (through the electrolyte) and

electrons (around the external circuit, in the opposite

direction) are interconnected processes, and if either stops

so does the other. If ions stop moving through the electrolyte

because the battery completely discharges, electrons can't

move through the outer circuit either—so you lose your

power. Similarly, if you switch off whatever the battery is

powering, the flow of electrons stops and so does the flow of

ions. The battery essentially stops discharging at a high rate

(but it does keep on discharging, at a very slow rate, even

with the appliance disconnected).

Unlike simpler batteries, lithium-ion ones have built in

electronic controllers that regulate how they charge and

discharge. They prevent the overcharging and overheating

that can cause lithium-ion batteries to explode in some

circumstances.

As their name suggests, lithium-ion batteries are all about

the movement of lithium ions: the ions move one way when

the battery charges (when it's absorbing power); they move

the opposite way when the battery discharges (when it's

supplying power):

46 During charging, lithium ions (yellow circles) flow from

the positive electrode (red) to the negative electrode

(blue) through the electrolyte (gray). Electrons also flow

from the positive electrode to the negative electrode, but

take the longer path around the outer circuit. The

electrons and ions combine at the negative electrode and

deposit lithium there.

47 When no more ions will flow, the battery is fully

charged and ready to use.

48 During discharging, the ions flow back through the

electrolyte from the negative electrode to the positive

electrode. Electrons flow from the negative electrode to

the positive electrode through the outer circuit, powering

your laptop. When the ions and electrons combine at the

 positive electrode, lithium is deposited there.

49 When all the ions have moved back, the battery is fully

discharged and needs charging up again.

This second animation shows what's going on in the battery

in a bit more detail. Again, the negative graphite electrode

(blue) is shown on the left, the positive cobalt-oxide

electrode (red) on the right, and the lithium ions are

represented by yellow circles. When the battery is fully

charged, all the lithium ions are stored between layers of

graphene (sheets of carbon one atom thick) in the graphite

electrode (they have all moved over to the left). In this

charged-up state, the battery is effectively a multi-layer

sandwich: graphene layers alternate with lithium ion layers.

As the battery discharges, the ions migrate from the

graphite electrode to the cobalt-oxide electrode (from left to

right). When it's fully discharged, all the lithium ions have

moved over to the cobalt-oxide electrode on the right. Once

again, the lithium ions sit in layers, in between layers of

cobalt ions (red) and oxide ions (blue). As the battery

charges and discharges, the lithium ions shunt back and

forth from one electrode to the other.

Generally, lithium ion batteries are more reliable than older

technologies such as nickel-cadmium (NiCd, pronounced

"nicad") and don't suffer from a problem known as the

"memory effect" (where nicad batteries appear to become

harder to charge unless they're discharged fully first). Since

lithium-ion batteries don't contain cadmium (a toxic, heavy

metal), they are also (in theory, at least) better for the

environment—although dumping any batteries (full of

metals, plastics, and other assorted chemicals) into landfills

is never a good thing. Compared to heavy-duty rechargeable

batteries (such as the lead-acid ones used to start cars),

lithium-ion batteries are relatively light for the amount of

energy they store.

If we're interested in the drawbacks of lithium-ion batteries,

it's important to bear in mind what we're comparing them

with. As a power source for automobiles, we really need to

compare them not with other types of batteries but with

gasoline. Despite considerable advances over the years, kilo

for kilo, rechargeable batteries still store only a fraction as

much energy as ordinary gas; in more scientific words, they

have a much lower energy density (they store less energy

per unit of weight). That also explains why you can fully

"recharge" (refuel) a gas-powered automobile in a couple of

minutes, whereas it'll generally take you hoursto recharge

the batteries in an electric car. Then again, you have to bear

in mind that these disadvantages are balanced by other

advantages, such as the greater fuel economy of electric

cars and their relative lack of air pollution (zero

tailpipe/exhaust emissions from the vehicle itself).

Photo: Lithium-ion (Li-ion) batteries can inflate like little cushions if they don't have a
means of venting any gases produced during charging (mainly carbon monoxide,
carbon dioxide, and hydrogen, though smaller amounts of other organic gases may
also be present). Here are two identical batteries from a cellphone, the top one of
which has almost doubled in width due to the trapped gases inside.

Leaving aside vehicles and considering lithium-ion batteries

more generally, what are the problems? The biggest issue is

safety: Li-ion batteries will catch fire if they're overcharged

or if an internal malfunction causes a short circuit; in both

cases, the batteries heat up in what's called a "thermal

runaway," eventually catching fire or exploding. That

problem is solved with a built-in circuit breaker, known as a

current interrupt device or CID, which kills the charging

current when the voltage reaches a maximum, if the

batteries get too hot, or their internal pressure rises too

high. But there remain concerns and, in 2016, the

International Civil Aviation Organization officially prohibited

shipments of lithium-ion batteries on passenger planes

because of the potential danger. Now the safety risks of

lithium batteries have attracted lots of media attention—

especially when they've caused fires to break out in electric

cars or on airplanes—but it's worth bearing in mind how few

incidents there have been given how common the

technology is (you'll find lithium-ion batteries in every

modern cellphone, laptop, tablet, and most other

rechargeable gadgets). And, once again, it's important to

bear in mind the risks of the alternatives: yes, lithium-ion

batteries in electric cars can catch fire—but gasoline-

powered automobiles catch fire much more often... and

cause actual explosions! Other types of batteries can also

catch fire and explode if they overheat, so fire isn't a

problem that's unique to lithium-ion technology.

What's the solution? One promising option, currently being

pioneered by a company called Ionic Materials, is to use

flame-resistant polymers (solid plastics) in place of the

flammable liquid electrolytes that are normally used in

lithium-ion batteries. Another option, favored by John

Goodenough, the chemist behind lithium-ion batteries, is to

use "doped" glass (treated to make it electrically conductive)

for the electrolyte instead. Time will tell whether one of

these options—or something else entirely—will topple

lithium-ion batteries from their place as the world's favorite

rechargeable technology.