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Lithium 9 volt, AA, and AAA sizes. The top object is a battery of three lithium-manganese dioxide cells; the bottom two are lithium-iron disulfide cells and are compatible with 1.5-volt alkaline cells.Lithium metal batteries are primary batteries that have metallic lithium as an anode. The name intentionally refers to the metal as to distinguish them from lithium-ion batteries, which use lithiated metal oxides as the cathode material.[1] Although most lithium metal batteries are non-rechargeable, rechargeable lithium metal batteries are also under development. Since , Dangerous Goods Regulations differentiate between lithium metal batteries (UN ) and lithium-ion batteries (UN ).[2]
They stand apart from other batteries in their high charge density 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.
Disposable primary lithium batteries must be distinguished from secondary lithium-ion or a lithium-polymer,[3] which are rechargeable batteries and contain no metallic lithium. Lithium is especially useful, because its ions can be arranged to move between the anode and the cathode, using an intercalated lithium compound as the cathode material but without using lithium metal as the anode material. Pure lithium will instantly react with water, or even moisture in the air; the lithium in lithium-ion batteries is a less reactive compound.
Lithium batteries are widely used in portable consumer electronic devices. The term "lithium battery" refers to a family of different lithium-metal chemistries, comprising many types of cathodes and electrolytes but all with metallic lithium as the anode. The battery requires from 0.15 to 0.3 kg (5 to 10 oz) of lithium per kWh. As designed these primary systems use a charged cathode, that being an electro-active material with crystallographic vacancies that are filled gradually during discharge.
Diagram of lithium button cell battery with MnO2 (manganese dioxide) at cathodeThe most common type of lithium cell used in consumer applications uses metallic lithium as the anode and manganese dioxide as the cathode, with a salt of lithium dissolved in an organic solvent as the electrolyte.[4]
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University of California San Diego have developed an electrolyte chemistry that allows lithium batteries to run at temperatures as low as -60 °C. The electrolytes also enable electrochemical capacitors to run as low as -80 °C. Previous low-temperature limit is -40 °C. High performance at room temperature is still maintained. This may improve energy density and safety of lithium batteries and electrochemical capacitors.[41]
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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.
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Small lithium batteries are very commonly used in small, portable electronic devices, such as PDAs, watches, camcorders, digital cameras, thermometers, calculators, personal computer BIOS (firmware),[42] 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. The common CR battery is 20 mm diameter and 3.2 mm thick, where the first two digits is the diameter and the last two digits are thickness. A CR is the same 20 mm diameter but 2.5 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.
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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.[43][44][45][46][dubious &#; discuss]
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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 . When the battery is made to contain more material, the separator can undergo stress.
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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 &#; especially if cobalt is present in the cells' design &#; can result in overheating of the battery (that lowers the electrical resistance of any cobalt content within the cell), rupture, and even an 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 an explosion.
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From January 1, , much stricter regulations 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 are restricted in some situations, particularly the transport of lithium batteries by air.
The United States Transportation Security Administration announced restrictions effective January 1, , 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.[47]
Australia Post prohibited transport of lithium batteries in air mail during .[48]
UK regulations for the transport of lithium batteries were amended by the National Chemical Emergency Centre in .[49]
In late , 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, United States, and Japan.[50][51][52]
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Unused lithium batteries provide a convenient source of lithium metal for use as a reducing agent in methamphetamine labs. Specifically, lithium metal reduces pseudoephedrine and ephedrine to methamphetamine in the Birch reduction method, which employs solutions of alkali metals dissolved in anhydrous ammonia.[53][54]
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 Wal-Mart stores were reported to limit the sale of disposable lithium batteries to three packages in Missouri and four packages in other states.[55]
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Button cell batteries are attractive to small children and are 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 and 12.5-fold increase in fatalities comparing the last decade to the previous one.[56][57]
KEEP OUT OF REACH OF CHILDREN icon required by IEC -4[58] on coin cells (lithium button cells) with 20 mm diameter or largerThe primary mechanism of injury with button battery ingestions is the generation of hydroxide ions, which cause severe chemical burns, at the anode.[59] This is an electrochemical effect of the intact battery, and does not require the casing to be breached or the contents released.[59] Complications include oesophageal strictures, tracheo-oesophageal fistulas, vocal cord paralysis, aorto-oesophageal fistulas, and death.[60] 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 CR lithium battery has been implicated in many of the complications from button battery ingestions by children of less than 4 years of age.[61]
While the only cure for an esophageal impaction is endoscopic removal, a study out of Children's Hospital of Philadelphia by Rachel R. Anfang and colleagues found that early and frequent ingestion of honey or sucralfate suspension prior to the battery's removal can reduce the injury severity to a significant degree.[57] As a result, US-based National Capital Poison Center (Poison Control) recommends the use of honey or sucralfate after known or suspected ingestions to reduce the risk and severity of injury to esophagus, and consequently its nearby structures.[62]
Button batteries can also cause significant necrotic injury when stuck in the nose or ears.[63] Prevention efforts in the US by the National Button Battery Task force in cooperation with industry leaders have led to changes in packaging and battery compartment design in electronic devices to reduce a child's access to these batteries.[64] However, there still is a lack of awareness across the general population and medical community to its dangers. Central Manchester University Hospital Trust warns that "a lot of doctors are unaware that this can cause harm".[65]
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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.[66] Most lithium batteries, are, however, classified as hazardous waste due to the possibility of fire. Another manufacturer states that while "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.[67]
The EPA, however, states that due to limited supply and increasingly high importance, lithium batteries should always be recycled if possible.[68] As well, a rupture in a battery poses a potential fire hazard, thus the EPA states that the average consumer should take lithium batteries to specialized lithium or hazardous materials facilities.
As lithium in used but non-working (i.e. 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. Some also alloy the lithium with magnesium (Mg) to cut costs.[citation needed]
Since there has been an exponential increase in demand for lithium batteries over time,[69] there have been pushes to find better ways to recycle lithium batteries.[70]
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A LOOK AT LITHIUM BATTERIES
In a prior article, Battery categories and chemistries, we discussed the two battery categories, primary batteries and secondary batteries, with a brief summary of the common batteries in each group. We focused on alkaline batteries in our post, Role of primary batteries, and presented the broad family of lithium-metal cells, which together with alkalines, dominate primary batteries in both popularity and usage.
n this article we will take a closer look at primary battery types and delve just a bit more in some of the more recognized lithium chemistries available. Excluded from this post are three primary battery types that serve niche applications&#;zinc-air batteries mainly used to power hearing-assisted devices, silver-oxide batteries mainly used for watches, and zinc-carbon batteries which were superseded by alkalines in the s but are still available for specialized needs. Available links to discussions on these batteries can be found at the end of this post.
Alkaline batteries have been with us since the s, invented in by Lewis Urry, a chemical engineer at the Eveready Battery Company. It served as the next step in off-the-shelf consumer batteries, gradually replacing the cheaper 1.5-volt zinc-carbon-battery that powered most consumer devices at its peak. Alkaline batteries deliver more energy at higher loads than their zinc-carbon predecessor and are considerably less susceptible to electrolyte leaks from spent batteries. Leaks are caused by the production of hydrogen gas all primary batteries produce as they discharge. In the absence of adequate venting, pressure builds that ruptures the battery seal creating a corrosive crystalline formation that spreads even into the device causing damage.
Compared to newer technologies, alkaline batteries deliver nearly 40 percent more energy than the typical lithium-io rechargeable battery but are not as strong on loading. Alkaline batteries are more suitable for low drain applications
Lithium batteries
Lithium batteries describe a family of varying cell chemistries. Some types, lithium-iron, are primary single-use batteries; others, are secondary rechargeable types known as lithium-ion. In common with each other, they use lithium for the anode (the negative electrode). Their principle difference lies in the material used for the cathode (the positive electrode), the most common of which is manganese, but could also consist of carbon, sulfur, polymer, or other material. In this section, we cover four of the more popular primary lithium-iron batteries.
Matching the 1.5-voltage of alkaline batteries, the lithium-iron disulfide is the newest addition to the primary lithium sub-family and can meet and exceed the needs of any application requiring 1.5-volt AAA or AA alkaline batteries. In most cases, it will outperform the alkaline cell in nearly every way. A lithium AA battery can outlasts an alkaline battery by up to six times when used in a high drain application such as a digital camera. It boasts a higher operating voltage, improved stability, and a lower resistance than standard alkaline cells. Additional advantages of the lithium-iron disulfide battery include low temperature performance and improved leak resistance, and a shelf life of 15 years due to its low self-discharge rate.
While on might be tempted to replace their spent alkaline batteries with this chemistry, as expected with all battery types, there are a few drawbacks. First, they do cost a bit more but still well-affordable. Second, their transport is restricted. Bulk shipments are prohibited by both the Department of Transportation (DOT) and the Federal Aviation Administration (FAA). With few exceptions, most airlines restrict quantities to two grams per passenger carryon. Li-FeS2 batteries contain about 0.98 grams of lithium per cell, which allows for just two spare batteries. These regulations reflect the dangers associated with mishandling of lithium batteries in general. Leaks and explosions can, under certain conditions, result from mismatching a depleted cell, adding a foreign cell, or even inserting it backwards in the battery bay.
Often found in horizontal drilling (i.e., fracking) applications because of its ability to withstand high vibration and heat generated, the lithium-thionyl chloride battery is among the toughest and most powerful lithium-metal batteries available. LTC batteries have a nominal voltage of 3.6 volts per cell, but like alkalines, their moderately high resistance limits their application to moderate discharge loads; however, the LTCs exceed 500Wh/kg (watt hours per kilogram) in specific energy rating, which means it offers twice the capacity of nearly any rechargeable Li-ion. The runtime of lithium-thionyl chloride batteries are additionally determined by other factors, including load pattern and thermal condition.
Due to safety concerns, LTC batteries are neither found in consumer devices, nor available as a civilian general-purpose battery. Their use is relegated primarily to industrial equipment, medical and sensor applications, and military devices such as mines and fuses. The potent chemistry of LTC batteries calls for handling by trained professionals.
Where LTCs fail to address consumer needs, the similar lithium-manganese dioxide battery is available for civilian use. In fact, it is the most commonly used primary lithium, dominating nearly 80% of the primary lithium battery market and produced by all major battery manufacturers. Among its advantages are its affordability, long service life, low-drain, and ability to also handle high pulse currents. The Li-M cell runs at 3&#;3.3V and a specific energy of well over half its LTC counterpart, or 280Wh/kg. It is typically used in sensors, medical devices, photography equipment, as well as watches. The prefix &#;C&#; in the common CR battery typically found on computer motherboards and watches, is a designation used to indicate its lithium chemistry. Usually, this coin cell battery is of the lithium-manganese dioxide chemistry.
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As with all lithium batteries, extra care must be exercised to protect them from short circuiting, electrical or physical abuse, and heat. Additional regulations apply to their transportation and disposal.
Lithium sulfur dioxide batteries are primarily used in defense applications that require large quantities of this battery, and medical devices such as cardiac defibrillators. It is a cylindrical shaped cell that delivers 2.8 volts in A, C, and D battery formats, and features a 5&#;10-year expected shelf life when properly stored at ambient room temperature. LiSo2 batteries are capable of delivering repeated power bursts, and like their siblings, boast a high energy density of 330Wh/kg. While lithium sulfur dioxide batteries are cost-effective to manufacture, they are increasingly being supplanted by the superior Li-M cell. The battery gets its name from its cathode which consists of porous carbon filled with sulfur dioxide.
A summary of the five, commonly used, primary batteries:
Chemisty
Alkaline
Lithium-iron disulfide
Lithium-thionyl chloride
Lithium-manganese dioxide
Lithium-sulfur dioxide
Chemical short name
N/A
LiFeS2
LiSOCI2 or LTC
LiMnO2 or Li-M
LiSo2
Specific energy
200Wh/kg
300Wh/kg
500Wh/kg
280Wh/kg
330Wh/kg
Voltage
1.5V
1.5V
3.6&#;3.9V
3&#;3.3V
2.8V
Power
Low
Moderate
Excellent
Moderate
Moderate
Passivation*
N/A
Moderate
Moderate
Moderate
Moderate
Safety
Good
Good
Precaution
Good
Precaution
Pricing
Low
Economical
Industrial
Economical
Industrial
Shelf life
10 years
15 years
10&#;20 years
10&#;20 years
5&#;10 years
Operating temperature
0°C to 60°C
0°C to 60°C
-55°C to 85°C, higher for short duration
-30°C to 60°C
or if enabled
-55°C to 90°C
-54°C to 71°C
Typical application
Consumer devices.
Replaces alkaline where higher power and extended runtime needed.
Fracking. Not for consumer use.
Meter sensing,
medical devices, road toll sensors, cameras.
Defense. Gradual migration to
LiMnO2.
Formats
Various cylindrical A, AA, AAA, AAAA, C, D, 9V; button and coin cells.
Mainly cylindrical AA and AAA.
Various cylindrical, cuboid, wafer.
Various cylindrical A, AA, C, D; button and coin cells; cuboid.
Primarily cylindrical A, C, and D.
*Passivation is a very thin, resistant layer that forms on the lithium anode surface that serves to inhibit lithium degradation and minimize the self-discharge rate of lithium batteries.
Please reference these posts for popular, niche-specific, primary batteries
Zinc-air batteries
link
Silver-oxide batteries
link
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