Lithium battery

This article is about disposable lithium batteries. It is not to be confused with Lithium-ion battery.
CR2032 lithium button cell battery
Lithium 9 volt, AA, and AAA sizes. The top unit has three lithium-manganese dioxide cells internally, the bottom two are lithium-iron disulfide single cells physically and electrically compatible with 1.5 volt zinc batteries.

Lithium batteries are disposable (primary) batteries that have lithium metal or lithium compounds as an anode.

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.

History

Description

The term "lithium battery" refers to a family of different chemistries, comprising many types of cathodes and electrolytes. The battery requires from 0.15 to 0.3 kg of lithium per kWh.

Diagram of lithium button cell battery with MnO2 (manganese dioxide) at cathode

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.

Inside pieces of a coin battery, refer to caption
Disassembled CR2032 battery From left — negative cup from inner side with layer of lithium (oxidized in air), separator (porous material), cathode (manganese dioxide), metal grid — current collector, metal casing (+) (damaged while opening the cell), on the bottom is plastic insulation ring

Another type of lithium cell having a large energy density is the lithium-thionyl chloride cell. Invented by Adam Heller in 1973, 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. This chemistry isn't rechargeable.[1] 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.

Chemistries

Chemistry Cathode Electrolyte Nominal voltage Open-circuit voltage Wh/kg Wh/L
Li-MnO2
(IEC code: C),
"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.[2] With discharge, the internal impedance rises and the terminal voltage decreases. High self-discharge at high temperatures.
Li-(CF)x
(IEC code: B),
"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.[2] 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.[3] 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.[4]
Li-FeS2
(IEC code: F),
"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[5] 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
(IEC code: E)		 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.[6] Not used for consumer or general-purpose batteries.
Li-SOCl2,BrCl, Li-BCX
(IEC code: E)		 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.[7]
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.[8] Used in military applications.

Addition of bromine monochloride can boost the voltage to 3.9 V and increase energy density.[9]

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.[10] 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.[11] Two-stage discharge with a plateau. Output voltage decreasing proportionally to the degree of discharge. Resistant to abuse.
Li-CuO
(IEC code: G),
"GR"		 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-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-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).[12] Discharging below the first plateau reduces the life of the cell.[12] The complex salt dissolved in SO2 has a lower vapor pressure at room temperature than pure sulfur dioxide,[13] making the construction simpler and safer than Li-SO2 batteries.
Li/Al-MnO2 Manganese dioxide 3 V[14]
Rechargeable. Also known as ML type.
Li/Al-V2O5 Vanadium pentoxide 3 V[15]
Rechargeable. Also known as VL type.
Li–air (Lithium–air battery) Porous carbon Organic, aqueous, glass-ceramic (polymer-ceramic composites) 1800–660 [16] 1600–600 [16]
Rechargeable. No commercial implementation is available as of 2012 due to difficulties in achieving multiple discharge cycles without losing capacity.[16] There are multiple possible implementations, each having different energy capacities, advantages and disadvantages. In November 2015, a team of University of Cambridge researchers furthered work on lithium-air batteries by developing a charging process capable of prolonging the battery life and battery efficiency. Their work resulted in a battery that delivered high energy densities, more than 90% efficiency, and could 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. They were first developed in a research environment by Abraham & Jiang in 1996.[17] 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.[18] 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.

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).

Applications

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,[19] 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.

Popularity

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.[20][21][22][23]

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.

Rapid-discharge problems

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.

Air travel

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.[24]

Australia Post prohibited transport of lithium batteries in air mail during 2010.[25]

UK regulations for the transport of lithium batteries were amended by the National Chemical Emergency Centre in 2009.[26]

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.[27][28][29]

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.[30]

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.[31]

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.[32] 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.[33] Button batteries can also cause significant necrotic injury when stuck in the nose or ears.[34]

Disposal

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.[35] 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.[36]

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.

See also

References

  1. ↑ "Single piece and bulk quantity Lithium thionyl chloride (LiSOCl2, Li/SOCl2)) Cells for sale from PowerStream". 2016-05-04. Retrieved 2016-05-05. Lithium thionyl Chloride (Li/SOCl2) cells have the highest energy density of any lithium battery. They are not rechargeable, but have extremely long shelf-life
  2. 1 2 http://www.panasonic.com/industrial/batteries-oem/oem/primary-coin-cylindrical/br-cr.aspx
  3. ↑ Greatbatch W, Holmes CF, Takeuchi ES, Ebel SJ (November 1996). "Lithium/carbon monofluoride (Li/CFx): a new pacemaker battery". Pacing Clin Electrophysiol 19 (11 Pt 2): 1836–40. doi:10.1111/j.1540-8159.1996.tb03236.x. PMID 8945052.
  4. ↑ "Lithium Poly Carbon Monoflouride". House Of Batteries.
  5. ↑ http://data.energizer.com/PDFs/l91.pdf
  6. ↑ Pilarzyk, Jim. "White Paper - Lithium Carbon Monofluoride Coin Cells in Real-Time Clock and Memory Backup Applications". rayovac.com. Rayovac Corporation. Archived from the original on 2007-12-12.
  7. ↑ "Lithium sulfuryl chloride battery". Corrosion-doctors.org. Retrieved 2011-01-19.
  8. ↑ McGraw, Jack (March 7, 1984). "Letter to Dick Bruner, U.S. Defense Logistics Agency". U.S. Environmental Protection Agency.
  9. ↑ "Lithium Batteries Specifications". Lithium-batteries.globalspec.com. Retrieved 2011-01-19.
  10. ↑ Mallela, V. S.; Ilankumaran, V.; Rao, N. S. (2004). "Trends in cardiac pacemaker batteries". Indian pacing and electrophysiology journal 4 (4): 201–212. PMC 1502062. PMID 16943934.
  11. ↑ Gonzalez, Lina (Summer 2005). "Solid State NMR Investigation of Silver Vanadium Oxide (SVO)". CUNY, Hunter College.
  12. 1 2 McDonald, R. C.; Harris, P.; Hossain, S.; Goebel, F. (1992). "Analysis of secondary lithium cells with sulfur dioxide based electrolytes". IEEE 35th International Power Sources Symposium. p. 246. doi:10.1109/IPSS.1992.282033. ISBN 0-7803-0552-3.
  13. ↑ US patent 4891281, Kuo, Han C. & Foster, Donald L., "Electrochemical cells having low vapor pressure complexed SO2 electrolytes", issued 01-02-1990, assigned to Duracell Inc.
  14. ↑ http://www.panasonic.com/industrial/batteries-oem/oem/rechargeable-coin/manganese-lithium.aspx
  15. ↑ http://www.panasonic.com/industrial/batteries-oem/oem/rechargeable-coin/vanadium-pentoxide.aspx
  16. 1 2 3 Christensen, J.; Albertus, P.; Sanchez-Carrera, R. S.; Lohmann, T.; Kozinsky, B.; Liedtke, R.; Ahmed, J.; Kojic, A. (2012). "A Critical Review of Li∕Air Batteries". Journal of the Electrochemical Society 159 (2): R1. doi:10.1149/2.086202jes.
  17. ↑ Abraham, K. M. (1996). "A Polymer Electrolyte-Based Rechargeable Lithium/Oxygen Battery". Journal of The Electrochemical Society 143 (1): 1. doi:10.1149/1.1836378. ISSN 0013-4651.
  18. ↑ Smith, Chris (November 2, 2015). "University of Cambridge researchers create new battery technology for first time ever". Yahoo Tech. Retrieved November 2, 2015.
  19. ↑ Torres, Gabriel (24 November 2004). "Introduction and Lithium Battery". Replacing the Motherboard Battery. hardwaresecrets.com. Retrieved June 20, 2013.
  20. ↑ "BAJ Website | Monthly battery sales statistics". Baj.or.jp. Retrieved 2013-06-12.
  21. ↑ INOBAT 2008 statistics
  22. ↑ Battery Waste Management - 2006 DEFRA
  23. ↑ "Battery Statistics". EPBAEurope.net. European Portable Battery Association. 2000. Archived from the original on 2012-03-21. Retrieved 2015-07-28.
  24. ↑ "Traveling Safe with Batteries". U.S. Department of Transportation. Retrieved 2007-12-29.
  25. ↑ "Customer guidelines for posting lithium batteries" (PDF). AusPost.com.au.
  26. ↑ "Lithium Battery Transport Regulation". The-NCEC.com.
  27. ↑ "Postage Guide - section 6.3" (PDF). Hong Kong Post.
  28. ↑ "349 Miscellaneous Hazardous Materials (Hazard Class 9)". Publication 52 - Hazardous, Restricted, and Perishable Mail. United States Postal Service. February 2015. Retrieved 2015-07-25.
  29. ↑ "I want to send a laptop to overseas. How can I do that ?". Post.JapanPost.jp. Retrieved 2011-01-19.
  30. ↑ Parker, Molly (January 26, 2004). "Meth fear cuts cold-pill access ; Pseudoephedrine used in illegal drug". Chicago Tribune. p. 1.(registration required)
  31. ↑ LItovitz, Toby; Whitaker N; Clark L; White NC; Marsolek M (June 2010). "Emerging battery-ingestion hazard: clinical implications.". Pediatrics 125 (6): 1168–77. doi:10.1542/peds.2009-3037. Retrieved 11 June 2011.
  32. ↑ "Parents warned after girl's battery death". Brisbane Times. AAP. July 2, 2013. Retrieved July 2, 2013.
  33. ↑ Litovitz, Toby; Whitaker N; Clark L. (June 2010). "Preventing battery ingestions: an analysis of 8648 cases.". Pediatrics 125 (6): 1178–83. doi:10.1542/peds.2009-3038. Retrieved 11 June 2011.
  34. ↑ Mack, Sharon Kiley, "Tiny lithium battery nearly kills Deer Isle toddler", Bangor Daily News, July 24, 2011 3:41 pm. Retrieved 2 August 2011
  35. ↑ Disposal of Energizer AA and AAA Lithium L92 and L92 Battery Lithium/Iron Disulfide, retrieved 2012 Aug 20
  36. ↑ Battery Disposal Guidelines

External links

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