They stand apart from other batteries in their high charge density (long life) and high cost per unit. Depending on the design and chemical compounds used, lithium cells can produce voltages from 1.5 V (comparable to a zinc–carbon or alkaline battery) to about 3.7 V.
By comparison, lithium-ion batteries are rechargeable batteries in which lithium ions move between the anode and the cathode, using an intercalated lithium compound as the electrode material instead of the metallic lithium used in lithium batteries.
Lithium batteries are widely used in products such as portable consumer electronic devices.
- 1 History
- 2 Description
- 3 Chemistries
- 4 Applications
- 5 Safety issues and regulation
- 6 Health issues on ingestion
- 7 Disposal
- 8 Latest technology: lithium-air batteries
- 9 See also
- 10 References
- 11 External links
Another type of lithium cell having a large energy density is the lithium-thionyl chloride cell. Invented by Adam Heller, 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 the consumer does not replace them. The cell contains a liquid mixture of thionyl chloride (SOCl2) and lithium tetrachloroaluminate (LiAlCl
4), which act as the cathode and electrolyte, respectively. A porous carbon material serves as a cathode current collector which receives electrons from the external circuit. Lithium-thionyl chloride batteries are well suited to extremely low-current applications where long life is necessary, such as wireless alarm systems.
|Chemistry||Cathode||Electrolyte||Nominal voltage||Open-circuit voltage||Wh/kg||Wh/L|
|Li-MnO2 ("CR")||Heat-treated manganese dioxide||Lithium perchlorate in propylene carbonate and dimethoxyethane||3 V||3.3 V||280||580|
|"Li-Mn". The most common consumer-grade lithium 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. Operational temperature ranges from -30 °C to 60 °C. Can deliver high pulse currents. With discharge, the internal impedance rises and the terminal voltage decreases. High self-discharge at high temperatures.|
|Li-(CF)x ("BR")||Carbon monofluoride||Lithium tetrafluoroborate in propylene carbonate, dimethoxyethane, or gamma-butyrolactone||3 V||3.1 V||360–500||1000|
|Cathode material formed by high-temperature intercalation of fluorine gas into graphite powder. Compared to manganese dioxide (CR), which has the same nominal voltage, it provides more reliability. Used for low to moderate current applications in memory and clock backup batteries. Used in aerospace applications, qualified for space since 1976, military applications both terrestrial and marine, in missiles, and in artificial cardiac pacemakers. Operates up to around 80 °C. Very low self-discharge (<0.5%/year at 60 °C, <1%/yr at 85 °C). Developed in the 1970s by Matsushita.|
|Li-FeS2 ("FR")||Iron disulfide||Propylene carbonate, dioxolane, dimethoxyethane||1.4–1.6 V||1.8 V||297|
|"Lithium-iron", "Li/Fe". Called "voltage-compatible" lithium, because it can work as a replacement for alkaline batteries with its 1.5 V nominal voltage. As such, Energizer lithium cells of AA and AAA size employ this chemistry. 2.5 times higher lifetime for high current discharge regime than alkaline batteries, better storage life due to lower self-discharge, 10–20 years storage time. FeS2 is cheap. Cathode often designed as a paste of iron sulfide powder mixed with powdered graphite. Variant is Li-CuFeS2.|
|Li-SOCl2||Thionyl chloride||Lithium tetrachloroaluminate in thionyl chloride||3.5 V||3.65 V||500–700||1200|
|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 V||3.95 V||330||720|
|Liquid cathode. Similar to thionyl chloride. Discharge does not result in build-up 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.
|Li-I2||Iodine that has been mixed and heated with poly-2-vinylpyridine (P2VP) to form a solid organic charge transfer complex.||A solid monomolecular layer of crystalline Lithium iodide that conducts lithium ions from the anode to the cathode but does not conduct Iodine.||2.8 V||3.1 V|
|Solid electrolyte. Very high reliability and low self discharge rate. Used in medical applications that need a long life, e.g. pacemakers. 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.|
|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, for example, 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, like implantable defibrillators, neurostimulators, and drug infusion systems. Also projected for use in other electronics, such as 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.|
|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 the mid-1990s, replaced by lithium-iron sulfide. Current use limited.|
|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-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||Lithium cobalt oxide|
|Li-NiCoO2||Lithium nickel cobalt oxide|
|Li-CuCl2||Copper chloride||LiAlCl4 or LiGaCl4 in SO2, a liquid, inorganic, non-aqueous electrolyte.|
|Rechargeable. This cell has three voltage plateaus as it discharges (3.3 V, 2.9 V and 2.5 V). Discharging below the first plateau reduces the life of the cell. The complex salt dissolved in SO2 has a lower vapor pressure at room temperature than pure sulfur dioxide, making the construction simpler and safer than Li-SO2 batteries.|
|Li/Al-MnO2||Manganese dioxide||3 V|
|Rechargeable. Also known as ML type.|
|Li/Al-V2O5||Vanadium pentoxide||3 V|
|Rechargeable. Also known as VL type.|
|Li–air (Lithium–air battery)||Porous carbon||Organic, aqueous, glass-ceramic (polymer-ceramic composites)||1800–660 ||1600–600 |
|Rechargeable. No commercial implementation is available as of 2012 due to difficulties in achieving multiple discharge cycles without losing capacity. There are multiple possible implementations, each having different energy capacities, advantages and disadvantages.|
The liquid organic electrolyte is a solution of an ion-forming inorganic lithium compound in a mixture of a high-permittivity solvent (propylene carbonate) and a low-viscosity solvent (dimethoxyethane).
Lithium batteries find application in many long-life, critical devices, such as 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 device. In such cases, an expensive lithium battery may not be cost-effective.
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 zinc cells.
Lithium batteries also prove valuable in oceanographic applications. While lithium battery packs are considerably more expensive than standard oceanographic packs, they hold up to three times the capacity of alkaline packs. The high cost of servicing remote oceanographic instrumentation (usually by ships) often justifies this higher cost.
Sizes and formats
Small lithium batteries are very commonly used in small, portable electronic devices, such as PDAs, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment and 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 1.6–4 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.
Lithium primary batteries account for 28% of all primary battery sales in Japan but only 1% of all battery sales in Switzerland. In the EU only 0.5% of all battery sales including secondary types are lithium primaries.
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 µm 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.
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 to prevent explosion.
From January 1, 2013 much stricter regulations for the carriage of Lithium batteries were introduced by IATA regarding the carriage of lithium batteries by air. They were adopted by the International Postal Union; however, some countries, e.g. the UK, have decided that they will not accept Lithium batteries unless they are included with the equipment they power.
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.
In late 2009, at least some postal administrations restricted airmail shipping (including Express Mail Service) of lithium batteries, lithium-ion batteries and products containing these (such as laptops and cell phones). Among these countries are Hong Kong, USA, and Japan.
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. In 2004 Wal-Mart stores were reported to limit the sale of disposable lithium batteries to three packages in Missouri and four packages in other states.
Health issues on ingestion
Button cell batteries are attractive to small children and often ingested. In the past 20 years, although there has not been an increase in the total number of button cell batteries ingested in a year, researchers have noted a 6.7-fold increase in the risk that an ingestion would result in a moderate or major complication.
The primary mechanism of injury with button battery ingestions is the generation of hydroxide ions, which cause severe chemical burns, at the anode. This is an electrochemical effect of the intact battery, and does not require the casing to be breached or the contents released. Complications include oesophageal strictures, Tracheo-oesophageal fistulas, vocal cord paralysis, aorto-oesophageal fistulas, and death. The majority of ingestions are not witnessed; presentations are non-specific; battery voltage has increased; the 20 to 25 mm button battery size are more likely to become lodged at the cricopharyngeal junction; and severe tissue damage can occur within 2 hours. The 3 V, 20 mm CR2032 lithium battery has been implicated in many of the complications from button battery ingestions by children of less than 4 years of age. Button batteries can also cause significant necrotic injury when stuck in the nose or ears.
Regulations for disposal and recycling of batteries vary widely; local governments may have additional requirements over those of national regulations. In the United States, one manufacturer of lithium iron disulfide primary batteries advises that consumer quantities of used cells may be discarded in municipal waste, as the battery does not contain any substances controlled by US Federal regulations. Another manufacturer states that "button" size lithium batteries contain perchlorate, which is regulated as a hazardous waste in California; regulated quantities would not be found in typical consumer use of these cells.
As lithium in used but non working (ie extended storage) button cells is still likely to be in the cathode cup, it is possible to extract commercially useful quantities of the metal from such cells as well as the manganese dioxide and specialist plastics. From experiment the usual failure mode is that they will read 3.2V or above but be unable to generate useful current (<5mA versus >40mA for a good new cell) Some also alloy the lithium with magnesium (Mg) to cut costs and these are particularly prone to the mentioned failure mode.
Latest technology: lithium-air batteries
In November of 2015, a team of University of Cambridge researchers announced the creation of a new battery technology capable of prolonging the battery life and battery efficiency by inventing a lithium-oxygen battery that uses graphene electrodes to offer high-density, more than 90% efficiency, and can be recharged for up to 2,000 times. The lithium-air batteries are described as the “ultimate” batteries because they propose a high theoretical energy density of up to ten times the energy offered by regular lithium-ion batteries. The technology, however, as of November 2015, will not be immediately available in any industry and it could take up to 10 years for lithium-air batteries to equip devices. The immediate challenge facing scientists involved in its invention is that the battery needs a special porous graphene electrode, among other chemical components, and a narrow voltage gap between charge and discharge to significantly increase efficiency.
- Battery holder
- Battery recycling
- High capacity oceanographic lithium battery pack
- Lithium as an investment
- Lithium ion manganese oxide battery
- Lithium ion polymer battery
- Lithium iron phosphate battery
- Lithium–sulfur battery
- Lithium–titanate battery
- Nanoarchitectures for lithium-ion batteries
- Thin film rechargeable lithium battery
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