Lithium battery

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CR2032 lithium button cell battery
Lithium 9 volt, AA, & AAA sizes

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 (same as zinc–carbon battery or alkaline battery) to about 3.7 V.[1] Lithium batteries are widely used in products such as portable consumer electronic devices.

Lithium primary batteries account for 28% of all primary battery sales in Japan but only 1% of all battery sales in Switzerland. In the UK and EU only 0.5% of all battery sales including secondary types are lithium primaries. [2] [3] [4] [5]

Contents

History

Description

The term "lithium battery" refers to a family of different chemistries, comprising many types of cathodes and electrolytes.

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. 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 (LiAlCl4), 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

ChemistryCathodeElectrolyteNominal voltageOpen-circuit voltageWh/kgWh/dm3
Li-MnO2 (Li-Mn, "CR")Heat-treated manganese dioxideLithium perchlorate in propylene carbonate and dimethoxyethane3 V3.3 V280580
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-SOCl2Thionyl chlorideLithium tetrachloroaluminate in thionyl chloride3.5 V3.65 V5001200
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]
Li-SOCl2,BrCl, Li-BCXThionyl chloride with bromine chlorideLithium tetrachloroaluminate in thionyl chloride3.7-3.8 V3.9 V350770
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-SO2Cl2Sulfuryl chloride3.73.95330720
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.[7]
Li-SO2Sulfur dioxide on teflon-bonded carbonLithium bromide in sulfur dioxide with small amount of acetonitrile2.85 V3.0 V250400
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-(CF)x ("BR")Carbon monofluorideLithium tetrafluoroborate in propylene carbonate, dimethoxyethane, and/or gamma-butyrolactone2.8 V3.1 V360680
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 in 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.[10] Maximum temperature 85 °C. Very low self-discharge (<0.5%/year at 60 °C, <1%/yr at 85 °C). Developed in 1970s by Matsushita.[11]
Li-I2Iodine 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.[12]2.8 V3.1 V
Solid electrolyte. Very high reliability and low self discharge rate. Used in medical applications that need a long life. 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-Ag2CrO4Silver chromateLithium perchlorate solution3.1/2.6 V3.45 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-CSVOSilver 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.[13] 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-CuOCopper(II) oxideLithium Perchlorate dissolved in Dioxolane1.5 V2.4 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)2Copper oxyphosphate
See Li-CuO
Li-CuSCopper sulfide1.5 V
Li-PbCuSLead sulfide and copper sulfide1.5 V2.2 V
Li-FeSIron sulfidePropylene carbonate, dioxolane, dimethoxyethane1.5-1.2 V
"Lithium-iron", "Li/Fe". used as a replacement for alkaline batteries. See lithium — iron disulfide.
Li-FeS2Iron disulfidePropylene carbonate, dioxolane, dimethoxyethane1.6-1.4 V1.8 V297
"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 due to lower self-discharge, 10 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-Bi2Pb2O5Lead bismuthate1.5 V1.8 V
Replacement of silver-oxide batteries, with higher energy density, lower tendency to leak, and better performance at higher temperatures.
Li-Bi2O3Bismuth trioxide1.5 V2.04 V
Li-V2O5Vanadium pentoxide3.3/2.4 V3.4 V120/260300/660
Two discharge plateaus. Low-pressure. Rechargeable. Used in reserve batteries.
Li-CoO2Lithium cobalt oxide
Li-NiCoO2Lithium nickel cobalt oxide
Li-CuCl2Copper chlorideLiAlCl4 or LiGaCl4 in SO2, a liquid, inorganic, non-aqueous electrolyte.
Rechargeable. This cell has three voltage plateaus as it discharges (3.3V, 2.9V and 2.5V).[14] Discharging below the first plateau reduces the life of the cell.[14] The complex salt dissolved in SO2 has a lower vapor pressure at room temperature than pure sulfur dioxide[15] making the construction simpler and safer than Li-SO2 batteries.
Li/Al-MnO2Manganese dioxide
Rechargeable.
Li/Al-V2O5Vanadium pentoxide
Rechargeable.
Li–air (Lithium–air battery)porous carbonorganic, aqueous, glass-ceramic (polymer-ceramic composites)
Rechargeable.

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 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 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.

CR2450.jpg

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.

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.

Ingestion and choking hazard

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.[16] The primary mechanism of injury with button battery ingestions is the generation of hydroxide ions at the anode. The hydroxide ions result in a chemical burn. Complications include oesophageal strictures, tracheo-oesophageal fistulas, vocal cord paralysis, aorto-oesophageal fistulas, and death. The reasons for the increasing frequency of devastating complications is complex. Public and physician awareness is poor, and many products using button batteries are not child-proofed. In fact, 61.8% of batteries that were ingested by young children were obtained from products. 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 in 2 hours. The 3 V, 20 mm lithium battery has been implicated in many of the complications from button battery ingestions by children less than 4 years of age.[17] Button batteries can also cause significant necrotic injury when stuck in the nose or ears.[18]

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. [19] 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. [20]

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 over current 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.[21]

Australia Post prohibited transport of lithium batteries in air mail during 2010.[22]

UK regulations for the transport of lithium batteries were amended[23] by the National Chemical Emergency Centre in 2009.

In late 2009, at least some postal administrations restricted airmail shipping (including EMS) of lithium batteries, lithium-ion batteries and products containing these ( such as laptops and cell phones). Among these countries are Hong Kong,[24] USA[25] and Japan.[26]

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.[27] High demand for lithium batteries for use in power-hungry devices such as digital cameras has conflicted with such restrictions in stores.

See also

References

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  2. ^ [1] Monthly battery sales statistics - MoETI - March 2011
  3. ^ [2] INOBAT 2008 statistics.
  4. ^ [3] Battery Waste Management - 2006 DEFRA
  5. ^ [4] EPBA statistics - 2000
  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. http://web.archive.org/web/20071212033213/http://www.rayovac.com/technical/wp_lithium.htm. 
  7. ^ "Lithium sulfuryl chloride battery". Corrosion-doctors.org. http://www.corrosion-doctors.org/PrimBatt/li-thionyl-sulfuryl.htm. Retrieved 2011-01-19. 
  8. ^ McGraw, Jack (March 7, 1984). "Letter to Dick Bruner, U.S. Defense Logistics Agency". U.S. Environmental Protection Agency. http://yosemite.epa.gov/OSW/rcra.nsf/Documents/CC7D81DF307086C085256611005AC8EC. 
  9. ^ "Lithium Batteries Specifications". Lithium-batteries.globalspec.com. http://lithium-batteries.globalspec.com/Specifications/Electrical_Electronic_Components/Batteries/Lithium_Batteries. Retrieved 2011-01-19. 
  10. ^ 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. PMID 8945052. 
  11. ^ "Lithium Poly Carbon Monoflouride". House Of Batteries. http://www.houseofbatteries.com/Howto/LiPolyC.htm. 
  12. ^ 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. //www.ncbi.nlm.nih.gov/pmc/articles/PMC1502062/.  edit
  13. ^ Gonzalez, Lina (Summer 2005). "Solid State NMR Investigation of Silver Vanadium Oxide (SVO)". CUNY, Hunter College. http://nyc-amp.cuny.edu/abstracts/view.asp?ID=654. 
  14. ^ a b 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. pp. 246. doi:10.1109/IPSS.1992.282033. ISBN 0-7803-0552-3.  edit
  15. ^ 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. 
  16. ^ LItovitz, Toby; Whitaker N, Clark L, White NC, Marsolek M (June 2010). "Emerging battery-ingestion hazard: clinical implications.". Pediatrics 125 (6): 1168–77. http://pediatrics.aappublications.org/content/125/6/1168.long. Retrieved 11 June 2011. 
  17. ^ Litovitz, Toby; Whitaker N, Clark L. (June 2010). "Preventing battery ingestions: an analysis of 8648 cases.". Pediatrics 125 (6): 1178–83. http://pediatrics.aappublications.org/content/125/6/1178.long. Retrieved 11 June 2011. 
  18. ^ Mack, Sharon Kiley, "Tiny lithium battery nearly kills Deer Isle toddler", Bangor Daily News, July 24, 2011 3:41 pm. Retrieved 2011-08-02.
  19. ^ ttp://data.energizer.com/PDFs/l91-l92_disp.pdf] Disposal of Energizer AA and AAA Lithium L92 and L92 Battery Lithium/Iron Disulfide, retrieved 2012 Aug 20
  20. ^ http://www.panasonic.com/industrial/batteries-oem/tertiary-navigation/product-information/battery-disposal.aspx Battery Disposal Guidelines
  21. ^ "Traveling Safe with Batteries". U.S. Department of Transportation. http://safetravel.dot.gov/whats_new_batteries.html. Retrieved 2007-12-29. 
  22. ^ "Customer guidelines for posting lithium batteries" (PDF). http://auspost.com.au/. http://auspost.com.au/media/documents/customer-guidelines-for-lithium-batteries.pdf. 
  23. ^ "Final Report - Lithium Batteries" (PDF). the-ncec.com. http://the-ncec.com/assets/NewsAndArticles/Final-report-version-2-Lithium-Batteries.pdf. 
  24. ^ "Postage Guide - section 6.3" (PDF). Hong Kong Post. http://www.hongkongpost.com/eng/publications/guide/content/6.3.pdf. 
  25. ^ Mark Ross (November 26, 2008). "Aviation Mail Security & Hazardous Materials". United States Postal Service. http://www.usps.com/aviationsecurity/. Retrieved 2011-01-19. 
  26. ^ "I want to send a laptop to overseas. How can I do that ? - Japan Post". Post.japanpost.jp. http://post.japanpost.jp/int/question/12_en.html. Retrieved 2011-01-19. 
  27. ^ Parker, Molly (January 26, 2004). "Meth fear cuts cold-pill access ; Pseudoephedrine used in illegal drug". Chicago Tribune. p. 1. http://pqasb.pqarchiver.com/chicagotribune/access/530679261.html?dids=530679261:530679261&FMT=ABS&FMTS=ABS:FT&type=current&date=Jan+26%2C+2004&author=Molly+Parker%2C+Tribune+staff+reporter&pub=Chicago+Tribune&desc=Meth+fear+cuts+cold-pill+access+%3B+Pseudoephedrine+used+in+illegal+drug&pqatl=google. (registration required)

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