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Lithium battery

Description

The term "lithium battery" refers to a family of different chemistries, comprising many types of cathodes and electrolytes. One type of lithium cell having a large energy density is the lithium-thionyl chloride cell. In this cell, a liquid mixture of thionyl chloride (SOCl2) and lithium tetrachloroaluminate (LiAlCl4) acts as the cathode and electrolyte respectively. A porous carbon material serves as a cathode current collector which receives electrons from the external circuit. However, lithium-thionyl chloride batteries are generally not sold to the consumer market, and find more use in commercial/industrial applications, or are installed into devices where no consumer replacement is performed. Lithium-thionyl chloride batteries are well suited to extremely low-current applications where long life is necessary, e.g. wireless alarm systems.

The most common type of lithium cell used in consumer applications uses metallic lithium as anode and manganese dioxide as cathode, with a salt of lithium dissolved in an organic solvent.

Disassembled CR2016 battery

1st: Anode cup, upside down, spent lithium partially scratched off

2nd: Separator, a thin layer of porous material soaked with electrolyte - lithium salt in an organic solvent

3rd: Cathode, a tablet of manganese dioxide

4th: Cathode can, with current collector (carbon layer) on its bottom and a gasket around its inner edge. Damaged by clumsy opening attempt.

Chemistries

Chemistry

Cathode

Electrolyte

Nominal voltage

Open-circuit voltage

Wh/kg

Wh/dm3

Li-MnO2 (Li-Mn, "CR")

Heat-treated manganese dioxide

Lithium perchlorate in propylene carbonate and dimethoxyethane

3 V

3.3 V

280

580

The most common consumer grade battery, about 80% of the lithium battery market. Uses inexpensive materials. Suitable for low-drain, long-life, low-cost applications. High energy density per both mass and volume. Can deliver high pulse currents. Wide temperature range. With discharge the internal impedance rises and the terminal voltage decreases. Maximum temperature limited to about 60 C. High self-discharge at high temperatures.

Li-SOCl2

Thionyl chloride

Lithium tetrachloroaluminate in thionyl chloride

3.5 V

3.65 V

290

670

Liquid cathode. For low temperature applications. Can operate down to -55 C, where it retains over 50% of its rated capacity. Negligible amount of gas generated in nominal use, limited amount under abuse. Has relatively high internal impedance and limited short-circuit current. High energy density, about 500 Wh/kg. Toxic. Electrolyte reacts with water. Low-current cells used for portable electronics and memory backup. High-current cells used in military applications. In long storage forms passivation layer on anode, which may lead to temporary voltage delay when put into service. High cost and safety concerns limit use in civilian applications. Can explode when shorted. Underwriters Laboratories require trained technician for replacement of these batteries. Hazardous waste, Class 9 Hazmat shipment.

Li-SOCl2,BrCl, Li-BCX

Thionyl chloride with bromine chloride

Lithium tetrachloroaluminate in thionyl chloride

3.7-3.8 V

3.9 V

350

770

Liquid cathode. A variant of the thionyl chloride battery, with 300 mV higher voltage. The higher voltage drops back to 3.5 V soon as the bromine chloride gets consumed during the first 10-20% of discharge. The cells with added bromine chloride are thought to be safer when abused.

Li-SO2Cl2

Sulfuryl chloride

3.7

3.95

330

720

Liquid cathode. Similar to thionyl chloride. Discharge does not result in buildup of elemental sulfur, which is thought to be involved in some hazardous reactions, therefore sulfuryl chloride batteries may be safer. Commercial deployment hindered by tendency of the electrolyte to corrode the lithium anodes, reducing the shelf life. Chlorine is added to some cells to make them more resistant to abuse. Sulfuryl chloride cells give less maximum current than thionyl chloride ones, due to polarization of the carbon cathode. Sulfuryl chloride reacts violently with water, releasing hydrogen chloride and sulfuric acid.

Li-SO2

Sulfur dioxide on teflon-bonded carbon

Lithium bromide in sulfur dioxide with small amount of acetonitrile

2.85 V

3.0 V

250

400

Liquid cathode. Can operate down to -55 C and up to +70 C. Contains liquid SO2 at high pressure. Requires safety vent, can explode in some conditions. High energy density. High cost. At low temperatures and high currents performs better than Li-MnO2. Toxic. Acetonitrile forms lithium cyanide, and can form hydrogen cyanide in high temperatures. Used in military applications.

Addition of bromine monochloride can boost the voltage to 3.9 V and increase energy density.

Li-(CF)x ("BR")

Carbon monofluoride

Lithium tetrafluoroborate in propylene carbonate, dimethoxyethane, and/or gamma-butyrolactone

2.8 V

3.1 V

360

680

Cathode material formed by high-temperature intercalation of fluorine gas into graphite powder. High energy density (250 Wh/kg), 7 year shelf life. Used for low to moderate current applications, eg. memory and clock backup batteries. Very good safety record. Used in aerospace applications, qualified for space since 1976. Used in military applications both terrestrial and marine, and in missiles. Also used in cardiac pacemakers. Maximum temperature 85 C. Very low self-discharge (<0.5%/year at 60 C, <1%/yr at 85 C). Developed in 1970s by Matsushita.

Li-I2

Iodine

solid organic charge transfer complex (eg. poly-2-vinylpyridine, P2VP)

2.8 V

3.1 V

Solid electrolyte. Very high reliability. Used in medical applications. Does not generate gas even under short circuit. Solid-state chemistry, limited short-circuit current, suitable only for low-current applications. Terminal voltage decreases with degree of discharge due to precipitation of lithium iodide. Low self-discharge.

Li-Ag2CrO4

Silver chromate

Lithium perchlorate solution

3.1/2.6 V

3.45 V

Very high reliability. Has a 2.6 V plateau after reaching certain percentage of discharge, provides early warning of impending discharge. Developed specifically for medical applications, eg. implanted pacemakers.

Li-Ag2V4O11, Li-SVO, Li-CSVO

Silver oxide+vanadium pentoxide (SVO)

lithium hexafluorophosphate or lithium hexafluoroarsenate in propylene carbonate with dimethoxyethane

Used in medical applications, eg. implantable defibrillators, neurostimulators, and drug infusion systems. Also projected for use in other electronics, eg. emergency locator transmitters. High energy density. Long shelf life. Capable of continuous operation at nominal temperature of 37 C. Two-stage discharge with a plateau. Output voltage decreasing proportionally to the degree of discharge. Resistant to abuse.

Addition of copper(II) oxide to the cathode material results in the Li-CSVO variant.

Li-CuO

Copper(II) oxide

Lithium Perchlorate dissolved in Dioxolane

1.5 V

2.4 V

Can operate up to 150 C. Developed as a replacement of zinc-carbon and alkaline batteries. "Voltage up" problem, high difference between open-circuit and nominal voltage. Produced until mid-1990s, replaced by lithium-iron sulfide. Current use limited.

Li-Cu4O(PO4)2

Copper oxyphosphate

See Li-CuO

Li-CuS

Copper sulfide

1.5 V

Li-PbCuS

Lead sulfide and copper sulfide

1.5 V

2.2 V

Li-FeS

Iron sulfide

Propylene carbonate, dioxolane, dimethoxyethane

1.5-1.2 V

"Lithium-iron", "Li/Fe". used as a replacement for alkaline batteries. See lithium - iron disulfide.

Li-FeS2

Iron disulfide

Propylene carbonate, dioxolane, dimethoxyethane

1.6-1.4 V

1.8 V

297

"Lithium-iron", "Li/Fe". Used in Energizer lithium cells as a replacement for alkaline zinc-manganese chemistry. Called "voltage-compatible" lithiums. 2.5 times higher lifetime for high current discharge regime than alkaline batteries, better storage life in e.g. cars in summer due to lower self-discharge, 10 years storage time. FeS2 is cheap. Some types rechargeable. Cathode often designed as a paste of iron sulfide powder mixed with powdered graphite. Variant is Li-CuFeS2.

Li-Bi2Pb2O5

Lead bismuthate

1.5 V

1.8 V

Replacement of silver-oxide batteries, with higher energy density, lower tendency to leak, and better performance at higher temperatures.

Li-Bi2O3

Bismuth trioxide

1.5 V

2.04 V

Li-V2O5

Vanadium pentoxide

3.3/2.4 V

3.4 V

120/260

300/660

Two discharge plateaus. Low-pressure. Rechargeable. Used in reserve batteries.

Li-CoO2

Cobalt dioxide

Li-CuCl2

Copper chloride

Rechargeable.

Li/Al-MnO2

Manganese dioxide

Rechargeable.

Li/Al-V2O5

Vanadium pentoxide

Rechargeable.

Li-ion

carbon

liquid

Rechargeable. See lithium ion battery.

Li-poly

polymer

solid

Rechargeable. See lithium ion polymer battery.

The liquid organic electrolyte is usually a solution of an ion-forming inorganic lithium compound in a mixture of a high-permittivity solvent (eg. propylene carbonate) and a low-viscosity solvent (eg. dimethoxyethane).

Applications

Lithium batteries find application in many long-life, critical devices, such as artificial pacemakers and other implantable electronic medical devices. These devices use specialized lithium-iodide batteries designed to last 15 or more years. But for other, less critical, applications such as in toys, the lithium battery may actually outlast the toy. In such cases, an expensive lithium battery is not cost-efficient.

Lithium batteries can be used in place of ordinary alkaline cells in many devices, such as clocks and cameras. Although they are more costly, lithium cells will provide much longer life, thereby minimizing battery replacement. However, attention must be given to the higher voltage developed by the lithium cells before using them as a drop-in replacement in devices that normally use ordinary cells.

Small lithium batteries are very commonly used in small, portable electronic devices, such as PDAs, watches, thermometers, and calculators, as backup batteries in computers and communication equipment, and in remote car locks. They are available in many shapes and sizes, with a common variety being the 3 volt "coin" type manganese variety, typically 20 mm in diameter and 1.64 mm thick. The heavy electrical demands of many of these devices make lithium batteries a particularly attractive option. In particular, lithium batteries can easily support the brief, heavy current demands of devices such as digital cameras, and they maintain a higher voltage for a longer period than alkaline cells.

Some other lithium batteries use a platinum-iridium alloy instead of more usual compounds. These batteries are generally not preferred, as their cost is high and they tend to be fragile.

Safety issues and regulation

The computer industry's drive to increase battery capacity can test the limits of sensitive components such as the membrane separator, a polyethylene or polypropylene film that is only 20-25 m thick. The energy density of lithium batteries has more than doubled since they were introduced in 1991. When the battery is made to contain more material, the separator can undergo stress.

Rapid-discharge issues

Lithium batteries can provide extremely high currents and can discharge very rapidly when short-circuited. Although this is useful in applications where high currents are required, a too-rapid discharge of a lithium battery can result in overheating of the battery, rupture, and even explosion. Lithium-thionyl chloride batteries are particularly susceptible to this type of discharge. Consumer batteries usually incorporate overcurrent or thermal protection or vents in order to prevent explosion.

Air travel

Because of the above risks, shipping and carriage of lithium batteries is restricted in some situations, particularly transport of lithium batteries by air.

The United States Transportation Security Administration announced restrictions effective January 1, 2008 on lithium batteries in checked and carry-on luggage. The rules forbid lithium batteries not installed in a device from checked luggage and restrict them in carry-on luggage by total lithium content.

Lithium batteries and methamphetamine labs

Unused lithium batteries provide a convenient source of lithium metal for use as a reducing agent in methamphetamine labs. Some jurisdictions have passed laws to restrict lithium battery sales or asked businesses to make voluntary restrictions in an attempt to help curb the creation of illegal meth labs. For example a newspaper article from January 2004 reports that Wal-Mart stores limit the sale of disposable lithium batteries to three packages in Missouri and four packages in other states. However, the heavy demand for lithium batteries for use in modern, current-hungry devices such as digital cameras conflicts with such restrictions. Via internet retailers, such restrictions can usually be bypassed with little effort.

Transportation

UK regulations for the transport of lithium batteries were amended by the National Chemical Emergency Centre in 2009.

See also

Lithium-ion battery

Lithium air battery

Lithium-ion polymer battery

Battery recycling

Battery holder

Button cell

References

^ http://www.protomatic.com/markets/alternative-energy/batteries Lithium Battery Production

^ Rayovac - White Papers

^ Lithium sulfuryl chloride battery

^ http://yosemite.epa.gov/OSW/rcra.nsf/Documents/CC7D81DF307086C085256611005AC8EC

^ Lithium Batteries Specifications

^ Lithium/carbon monofluoride (Li/CFx): a new pacema...[Pacing Clin Electrophysiol. 1996] - PubMed Result

^ Lithium Poly Carbon Monoflouride http://www.houseofbatteries.com/Howto/LiPolyC.htm

^ http://nyc-amp.cuny.edu/abstracts/view.asp?ID=654

^ "Traveling Safe with Batteries". Department of Transportation. http://safetravel.dot.gov/whats_new_batteries.html. Retrieved 2007-12-29. 

^ http://www.unknownnews.net/040126waronthinking.html

^ http://the-ncec.com/assets/NewsAndArticles/Final-report-version-2-Lithium-Batteries.pdf

Common back up circuit diagram

External links

The 2009 amendments to the regulations regarding transport of Lithium Batteries

Lithium Battery Emergency Line

Lithium Iron Phosphate Battery information

Properties of non-rechargeable lithium batteries

Brand Neutral Drawings of Lithium Batteries based on ANSI Specifications

Lithium Thionyl Chloride Battery MSDS and supporting safety information

v  d  e

Galvanic cells

Non-rechargeable:

primary cells

Alkaline battery  Aluminium battery  Bunsen cell  Chromic acid cell  Clark cell  Daniell cell  Dry cell  Grove cell  Leclanch cell  Lithium battery  Mercury battery  Nickel oxyhydroxide battery  Silver-oxide battery  Weston cell  Zamboni pile  Zinc-air battery  Zinc-carbon battery

Rechargeable:

secondary cells

Air-fueled lithium-ion battery  Lead-acid battery  Lithium-ion battery  Lithium-ion polymer battery  Lithium iron phosphate battery  Lithium sulfur battery  Lithium-titanate battery  Nickel-cadmium battery  Nickel hydrogen battery  Nickel-iron battery  Nickel-metal hydride battery  Low self-discharge NiMH battery  Nickel-zinc battery  Rechargeable alkaline battery  Sodium-sulfur battery  Vanadium redox battery  Zinc-bromine battery

Kinds of cells

Battery  Concentration cell  Flow battery  Fuel cell  Trough battery  Voltaic pile

Parts of cells

Anode  Catalyst  Cathode  Electrolyte  Half cell  Ions  Salt bridge  Semipermeable membrane

Categories: Disposable batteries | Lithium | Canadian inventions | Recyclable materials
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