Lithium-Ion Battery - Wikipedia, The Free Encyclopedia
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Lithium-ion battery
Nokia Li-ion battery for powering a mobile phone
Specific energy100265 Wh/kg[1][2]
(0.360.95 MJ/kg)
Energy density250730 Wh/L[2]
(0.902.23 MJ/L)
Specific power ~250-~340 W/kg[1]
Charge/discharge
efficiency
8090%[3]
Energy/consumer-
price
2.5 Wh/US$
Self-discharge rate 8% at 21 C15% at 40 C
31% at 60 C
(per month)[4]
Cycle durability4001200 cycles
[5]
Nominal cell voltage NMC 3.6 / 3.7 V,
LiFePO4 3.2 V
Lithium-ion batteryrom Wikipedia, the free encyclopedia
lithium-ion battery (sometimes Li-ion battery orLIB) is aember of a family of rechargeable battery types in which lithium
ons move from the anode to the cathode during discharge andack when charging. Li-ion batteries use an intercalated lithium
compound as the electrode material, compared to the metallicithium used in non-rechargeable lithium battery.
ithium-ion batteries are common in consumer electronics. Theyare one of the most popular types of rechargeable battery forortable electronics, with one of the best energy densities, noemory effect (note, however, that new studies have shown signs
of memory effect in lithium-ion batteries [6]), and only a slow lossof charge when not in use. Beyond consumer electronics, LIBsare also growing in popularity for military, electric vehicle and
aerospace applications.
[7]
For example, Lithium-ion batteries areecoming a common replacement for the lead acid batteries thatave been used historically for golf carts and utility vehicles.nstead of heavy lead plates and acid electrolyte, the trend is tose a lightweight lithium/carbon anode and lithium iron phosphate
cathode. Lithium-ion batteries can provide the same voltage asead-acid batteries, so no modification to the vehicle's drivesystem is required.[8]
Chemistry, performance, cost and safety characteristics varyacross LIB types. Handheld electronics mostly use LIBsbased
on lithium cobalt oxide (LiCoO2), which offers high energydensity, but present safety risks, especially when damaged.
ithium iron phosphate (LFP), lithium manganese oxide (LMO)and lithium nickel manganese cobalt oxide (NMC) offer lowerenergy density, but longer lives and inherent safety. Such batteriesare widely used for electric tools, medical equipment and otheroles. NMC inparticular is aleading contender for automotive
applications. Lithium nickel cobalt aluminum oxide (NCA) andithium titanate (LTO) are specialty designs aimed at particulariche roles.
ithium-ion batteries can be dangerous under some conditionsand can pose a safety hazard since they contain, unlike other rechargeable batteries, a flammable electrolyte and arealso kept pressurized. This makes the standards of these batteries high, and it consists of many safety features. Thereave been many reported accidents as well as recalls done by some companies.
Contents
1 History
1.1 Modern batteries2 Construction
2.1 Formats3 Electrochemistry
3.1 Electrolytes
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Varta lithium-ion battery, Museum
Autovision, Altlussheim, Germany
4 Charge and discharge5 Charging procedure6 Specifications7 Materials used in construction
7.1 Cathode7.2 Anode7.3 Electrolyte
8 Uses9 Self-discharge10 Battery life
10.1 Conditioning10.2 Multicell devices
11 Safety11.1 Environmental concerns and recycling11.2 Recalls11.3 Transport restrictions
12 Research
12.1 Tin electrodes12.2 Extrusion13 See also14 References15 Bibliography16 External links
istory
See also: History of the battery
ithium batteries were first proposed by M. S. Whittingham, now atinghamton University, while working for Exxon in the 1970s.[9] Whittinghamsed titanium(IV) sulfide and lithium metal as the electrodes.
eversible intercalation in graphite[10][11] and intercalation into cathodicoxides[12][13] was discovered in the 1970s by J. O. Besenhard at TU
unich. Besenhard proposed its application in lithium cells.[14][15] Electrolytedecomposition and solvent co-intercalation into graphite were severe early
drawbacks for battery life.
rimary lithium batteries with metallic lithium anodes pose safety issues. As aesult, lithium-ion batteries were developed in which both electrodes are
ade of a material containing lithium ions.[citation needed]
t Oxford University, England, in 1979, John Goodenough and Koichi Mizushima demonstrated a rechargeable cell
ith voltage in the 4 V range using lithium cobalt oxide (LiCoO 2) as the positive electrode and lithium metal as the
egative electrode.[16] This innovation provided the cathode material that made LIBs possible. LiCoO2 is a stableositive electrode material which acts as a donor of lithium ions, which means that it can be used with a negative
electrode material other than lithium metal. By enabling the use of stable and easy-to-handle negative electrode
aterials, LiCoO2 opened a whole new range of possibilities for novel rechargeable battery systems.
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n 1977, Samar Basu demonstrated electrochemical intercalation of lithium in graphite at the University ofennsylvania.[17][18] This led to the development of a workable lithium intercalated graphite electrode at Bell Labs
(LiC6)[19] to provide an alternative to the lithium metal electrode battery.
n 1980, Rachid Yazami demonstrated the reversible electrochemical intercalation of lithium in graphite.[20][21] Theorganic electrolytes available at the time would decompose during charging with a graphite anode, slowing thedevelopment of a rechargeable lithium/graphite battery. Yazami used a solid electrolyte to demonstrate that lithium coulde reversibly intercalated in graphite through an electrochemical mechanism. The graphite electrode discovered by
azami is currently the most commonly used electrode in commercial lithium ion batteries.
n 1983, Michael M. Thackeray, Goodenough, and coworkers identified manganese spinel as a cathode material. [22]
Spinel showed great promise, given its low-cost, good electronic and lithium ion conductivity, and three-dimensionalstructure, which gives it good structural stability. Although pure manganese spinel fades with cycling, this can beovercome with chemical modification of the material.[23] As of 2013 manganese spinel was used in commercial cells.[24]
n 1985, Akira Yoshino assembled a prototype cell using carbonaceous material into which lithium ions could be
nserted as one electrode, and lithium cobalt oxide (LiCoO2), which is stable in air, as the other.[25] By using materials
ithout metallic lithium, safety was dramatically improved. LiCoO2) enabled industrial-scale production and represents
he birth of the current lithium-ion battery.
n June 2012 John Goodenough, Rachid Yazami and Akira Yoshino received the 2012 IEEE Medal for Environmentaland Safety Technologies for developing the lithium ion battery.
odern batteries
n 1989, Goodenough and Arumugam Manthiram of the University of Texas at Austin showed that cathodes containingolyanions, e.g., sulfates, produce higher voltages than oxides due to the induction effect of the polyanion. [26]
n 1991, Sony and Asahi Kasei released the first commercial lithium-ion battery.
n 1996, Goodenough, Akshaya Padhi and coworkers proposed lithium iron phosphate (LiFePO4) and other phospho-olivines (lithium metal phosphates with the same structure as mineral olivine) as cathode materials.[27]
n 2002, Yet-Ming Chiang and his group at MIT showed a substantial improvement in the performance of lithiumatteries by boosting the material's conductivity by doping it[citation needed] with aluminium, niobium and zirconium. The
exact mechanism causing the increase became the subject of widespread debate.[28]
n 2004, Chiang again increased performance by utilizing iron phosphate particles of less than 100 nanometers indiameter. This decreased particle density almost one hundredfold, increased the cathode's surface area and improved
capacity and performance. Commercialization led to a rapid growth in the market for higher capacity LIBs, as well as aatent infringement battle between Chiang and Goodenough.[28]
s of 2011, lithium-ion batteries accounted for 66% of all portable secondary (i.e., rechargeable) battery sales inapan.[29]
Construction
The three primary functional components of a lithium-ion battery are the anode, cathode and electrolyte. Generally, theanode of a conventional lithium-ion cell is made from carbon. The cathode is a metal oxide, and the electrolyte is a
ithium salt in an organic solvent.[30] The electrochemical roles of the electrodes reverse between anode and cathode,depending on the direction of current flow through the cell.
The most commercially popular anode is graphite. The cathode is generally one of three materials: a layered oxide (suchas lithium cobalt oxide), a polyanion (such as lithium iron phosphate) or a spinel (such as lithium manganese oxide).[31]
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Cylindrical 18650 lithium ironphosphate cell before closing
Nissan Leaf's lithium-ion battery
pack.
The electrolyte is typically a mixture of organic carbonates such as ethylene carbonate or diethyl carbonate containingcomplexes of lithium ions.[32] These non-aqueous electrolytes generally use non-coordinating anion salts such as lithium
exafluorophosphate (LiPF6), lithium hexafluoroarsenate monohydrate (LiAsF6), lithium perchlorate (LiClO4), lithium
etrafluoroborate (LiBF4) and lithium triflate (LiCF3SO3).
epending on materials choices, the voltage, energy density, life and safety of a lithium-ion battery can changedramatically. Recently, novel architectures using nanotechnology have beenemployed to improve performance.
ure lithium is highly reactive. It reacts vigorously with water to form lithiumydroxide and hydrogen gas. Thus, a non-aqueous electrolyte is typicallysed, and a sealed container rigidly excludes moisture from the battery pack.
ithium ion batteries are more expensive than NiCd batteries but operateover a wider temperature range with higher energy densities. They require arotective circuit to limit peak voltage.
or notebooks or laptops, lithium-ion cells are supplied as part of a batteryack with temperature sensors, voltage converter/regulator circuit, voltageap, battery charge state monitor and the main connector. These componentsonitor the state of charge and current in and out of each cell, capacities of
each individual cell (drastic change can lead to reverse polarities which isdangerous),[33] temperature of each cell and minimize the risk of short circuits.[34]
Formats
i-ion cells are available in various form factors, which can generally bedivided into four groups:[35][36]
Small cylindrical (solid body without terminals, such as laptopbatteries)Large cylindrical (solid body with large threaded terminals)Pouch (soft, flat body, such as those used in cell phones)Prismatic (semi-hard plastic case with large threaded terminals, such asvehicles' traction packs)
The absence of a case gives pouch cells the highest energy density; however, pouch cells (and prismatic cells) require anexternal means of containment to prevent expansion when their state-of-charge (SOC) level is high.[37]
lectrochemistry
The three participants in the electrochemical reactions in a lithium-ion battery are the anode, cathode and electrolyte.
oth electrodes allow lithium ions to migrate towards and away from them. During insertion (orintercalation) ionsove into the electrode. During the reverse process, extraction (ordeintercalation), ions move back out. When a
ithium-based cell is discharging, the positive ion is extracted from the anode (usually graphite) and inserted into thecathode (lithium containing compound). When the cell is charging, the reverse occurs.
seful work is extracted when electrons flow through a closed external circuit. The following equations show one
example of the chemistry, in units of moles, making it possible to use coefficient .
The positive electrode half-reaction is:[38]
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The negative electrode half-reaction is:
The overall reaction has its limits. Overdischarge supersaturates lithium cobalt oxide, leading to the production of lithiumoxide,[39] possibly by the following irreversible reaction:
Overcharge up to 5.2 volts leads to the synthesis of cobalt(IV) oxide, as evidenced by x-ray diffraction:[40]
n a lithium-ion battery the lithium ions are transported to and from the cathode or anode by oxidizing the transition
etal, cobalt (Co), in from Co3+
to Co4+
during charging, and reduced from Co4+
to Co3+
duringdischarge.
The cell's energy is equal to the voltage times the charge. Each gram of lithium represents Faraday's constant/6.941 or13,901 coulombs. At 3 V, this gives 41.7 kJ per gram of lithium, or 11.6 kWh per kg. This is a bit more than the heatof combustion of gasoline, but does not consider the other materials that go into a lithium battery and that make lithiumatteries many times heavier per unit of energy.
Electrolytes
The cell voltages given in the Electrochemistry section are larger than the potential at which aqueous solutions canelectrolyze. Given lithium's high reactivity to water, nonaqueous or aprotic solutions are used.
iquid electrolytes in lithium-ion batteries consist of lithium salts, such as LiPF6, LiBF4 or LiClO4 in an organic solvent,such as ethylene carbonate, dimethyl carbonate, and diethyl carbonate. A liquid electrolyte acts as a carrier between the
cathode and the anode when current flows through an external circuit. Typical conductivities of liquid electrolyte at rooemperature (20 C (68 F)) are in the range of 10 mS/cm (1 S/m), increasing by approximately 3040% at 40 C
(104 F) and decreasing slightly at 0 C (32 F)[41]
Organic solvents easily decompose on anodes during charging. However, when appropriate organic solvents are usedas the electrolyte, the solvent decomposes on initial charging and forms a solid layer called the solid electrolytenterphase (SEI),[42] which is electrically insulating yet provides significant ionic conductivity. The interphase preventsdecomposition of the electrolyte after the second charge. For example, ethylene carbonate is decomposed at a relativelyigh voltage, 0.7 V vs. lithium, and forms a dense and stable interface.[43]
Composite electrolytes based on POE (poly(oxyethylene)) developed by Syzdek et al., provide a relatively stablenterface[44][45] It can be either solid (high molecular weight) and be applied in dry Li-polymer cells, or liquid (lowolecular weight) and be applied in regular Li-ion cells.
oom temperature ionic liquids (RTILs)are another approach to limiting the flammability and volatility of organicelectrolytes.[46]
Charge and discharge
uring discharge, lithium ions Li+
carry the current from the negative to the positive electrode, through the non-aqueous
electrolyte and separator diaphragm.[47]
uring charging, an external electrical power source (the charging circuit) applies an over-voltage (a higher voltage butof the same polarity) than that produced by the battery, forcing the current to pass in the reverse direction. The lithiumons then migrate from the positive to the negative electrode, where they become embedded in the porous electrode
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aterial in a process known as intercalation.
Charging procedure
The charging procedures for single Li-ion cells, and complete Li-ion batteries, are slightly different.
A single Li-ion cell is charged in 2 stages:[33]
1. CC2. CV
A Li-ion battery (a set of Li-ion cells in series) is charged in 3 stages:[48]
1. CC2. Balance (not required once a battery is balanced)3. CV
CC: Apply charging current to the battery, until the voltage limit per cell is reached.
alance: Reduce the charging current (or cycle the charging on and off to reduce the average current) while the state ofcharge of individual cells is brought to the same level by a balancing circuit, until the battery is balanced. Some fastchargers skip this stage.
CV: Apply a voltage equal to the maximum cell voltage times the number of cells in series to the battery, as the currentgradually declines asymptotically towards 0, until the current is below a set threshold of about 3% of initial constantcharge current.
eriodic topping charge about once per 500 hours. Top charging is recommended to be initiated when voltage goeselow 4.05 V/cell.
ithium-ion is charged at approximately 4.2 0.05 V/cell except for "military long life" that uses 3.92 V to extendattery life. Most protection circuits cut off if voltage greater than 4.3 V or temperature greater than 90 C is reached.elow 2.50 V/cell the battery protection circuit may render the battery unchargeable with regular charging equipment.ost battery circuits stop at 2.73.0 V/cell.
ailure to follow current and voltage limitations can result in an explosion. [49]
Specifications
Specific energy density: 150 to 250 Wh/kg (540 to 900 kJ/kg)[1]Volumetric energy density: 250 to 620 Wh/l (900 to 1900 J/cm)[2]
Specific power density: 300 to 1500 W/kg (@ 20 seconds and 285 Wh/l)[1]
ecause lithium-ion batteries can have a variety of cathode and anode materials, the energy density and voltage varyaccordingly.
They have a high open circuit voltage in comparison to aqueous batteries (such as lead acid, nickel-metal hydride and
ickel-cadmium).[50] The internal resistance of widely-used LiCoO2 batteries is higher than that of nickel-metal hydride,
ickel-cadmium, and LiFePO4 and lithium-polymer cells.[51] Internal resistance increases with both cycling and
age.[50][52] Rising internal resistance causes the voltage at the terminals to drop under load, which reduces the maximumcurrent draw. Eventually increasing resistance means that the battery can no longer operate for an adequate period.
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Cathode
Technology Researchers Target application Date Benefit
Manganesespinel (LMO)
Lucky Goldstar Chemical,[54]
NEC, Samsung,[24] Hitachi,[55]
Nissan/AESC[56], EnerDel[57]
Hybrid electric vehicle, cellphone, laptop
1996 durability, cost
Lithium ironphosphate
University of Texas/Hydro-
Qubec,[58]
/Phostech LithiumInc., Valence Technology,
A123Systems/MIT[59][60]
Segway Personal Transporter,
power tools, aviation products,automotive hybrid systems,PHEV conversions
1996
moderate density (2 Ah
outputs 70 amperes)operating temperature>60 C (140 F)
Lithium nickelmanganesecobalt (NMC)
Imara Corporation, Nissan
Motor,[61][62] Microvast Inc.2008 density, output, safety
LithiumManagneseOxide/NMC
Sony, Sanyo[63]power, safety (althoughlimited durability)
Lithium ironfluorophosphate
University of Waterloo[64] 2007 durability, cost (replace Liwith Na or Na/Li)
5% Vanadium-doped lithiumiron phosphateolivine
Binghamton University[65] 2008 output
Lithiumpurpurin
Arava Leela Mohana Reddy
Rice University[66]2012
Organic material, lowproduction cost90 milliamp hours per gram
after 50 charge/dischargecycles
Lithiummanganesedioxide on
porous tin
University of Illinois at Urbana-
Champaign[67]automotive, electronics 2013
energy density, power, fastcharge usingmicrostructured porous tin
Air IBM, Polyplus[68] Automotive 2012
Energy density: up to10,000 mAh per gram ofcathode material.
Rechargeable.
AirUniversity of Dayton Research
Institute[69][70]automotive 2009 density, safety
Water Polyplus Corporation[71][72] Marine 2012
Energy density: 1300wh/kg Non-rechargeable.Solid lithium anode. Solidelectrolyte. Reduced self-discharge.
node
Anode
Technology Density Durability ResearchersTarget
applicationDate Benefit
http://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-72http://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-71http://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-70http://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-69http://en.wikipedia.org/wiki/University_of_Dayton_Research_Institutehttp://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-68http://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-ms1-67http://en.wikipedia.org/wiki/University_of_Illinois_at_Urbana-Champaignhttp://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-66http://en.wikipedia.org/wiki/Rice_Universityhttp://en.wikipedia.org/wiki/1,2,4-Trihydroxyanthraquinonehttp://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-65http://en.wikipedia.org/wiki/Binghamton_Universityhttp://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-64http://en.wikipedia.org/wiki/University_of_Waterloohttp://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-63http://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-62http://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-61http://en.wikipedia.org/wiki/Nissan_Motorhttp://en.wikipedia.org/w/index.php?title=Lithium_nickel_manganese_cobalt&action=edit&redlink=1http://en.wikipedia.org/wiki/PHEVhttp://en.wikipedia.org/wiki/Segway_Personal_Transporterhttp://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-60http://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-59http://en.wikipedia.org/wiki/MIThttp://en.wikipedia.org/wiki/A123Systemshttp://en.wikipedia.org/wiki/Valence_Technologyhttp://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-58http://en.wikipedia.org/wiki/Hydro-Qu%C3%A9bechttp://en.wikipedia.org/wiki/University_of_Texashttp://en.wikipedia.org/wiki/Laptophttp://en.wikipedia.org/wiki/Cell_phonehttp://en.wikipedia.org/wiki/Hybrid_electric_vehiclehttp://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-57http://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-56http://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-55http://en.wikipedia.org/wiki/Hitachihttp://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-IEEELiRoad-24http://en.wikipedia.org/wiki/Samsunghttp://en.wikipedia.org/wiki/NEChttp://en.wikipedia.org/wiki/Lithium-ion_battery#cite_note-54http://en.wikipedia.org/wiki/LG_Chem -
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Lithium-titanate
battery (LT)
9,000Altairnano,
Microvast Inc.
automotive(PhoenixMotorcars),electrical grid(PJMInterconnectionRegionalTransmissionOrganization
control area,[73]
United StatesDepartment of
Defense[74]),bus (Proterra)
2008
output, chargingtime, durability (,safety, operating
temperature (-5070 C (-58
158 F)[75]
Lithium vanadiumoxide
745Wh/l Samsung/Subaru.[76] automotive 2007 density[77]
Cobalt-oxidenanowires fromgenetically modifiedvirus
MIT 2006density,
thickness[78]
Three-dimensional(3D) porous particlescomposed of curved2D nanolayers
specific energy>2000 mAh/g
Georgia Institute ofTechnology
high energybatteries forelectronics andelectricalvehicles
2011
high efficiency,rapid low-cost
synthesis[79]
Iron-phosphate
nanowires fromgenetically modifiedvirus
MIT 2009 density, thickness,self-
assembly[80][81][82]
Silicon/titaniumdioxide compositenanowires fromgenetically modified
tobacco virus
2000mAh/g 150University ofMaryland
explosivedetectionsensors,
biomimeticstructures,water-repellent
surfaces,micro/nanoscaleheat pipes
2010density, low
charge time[83]
Silicon whisker oncarbon nanofibercomposite
800-1000mAh/g
Junqing Ma,Physical sciences,Inc.
portableelectronics,electricalvehicles,electrical grid
2009
high capacity,good cycle life,fast rate, low
charge time[84]
Silicon nanowires onstainless steel
4,200 mAh/g Stanford Universitywireless sensorsnetworks,
2007
circumvents
swelling[85][86](shift from anode-to cathode-limited), durability
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issue remains (wirecracking)
Silicon oxide-coateddouble-walled siliconnanotubes
6,000Yi Cui/Stanford
University[87][88]Automotive andelectronics
2012
Metal hydrides 1480 mAh/g
Laboratoire deRactivit et de
Chimie des Solides,General Motors
2008[89]
Silicon nanotubes (orsilicon nanospheres)confined within rigidcarbon outer shells
2400 mAh/g
Georgia Institute ofTechnology, MSE,
NanoTech Yushin's
group[90]
stable highenergy batteriesfor cell phones,laptops,netbooks,radios, sensorsand electrical
vehicles
2010
ultra-highCoulombicEfficiency andoutstanding SEI
stability[91]
Silicon nanopowderin a conductive
polymer binder1400 mAh/g
Lawrence BerkeleyNational Laboratory[92]
Automotive andElectronics
2011
Compatible withcommercial Si,good cyclingcharacteristics
Silicon oxycarbide-coated carbonnanotubes
~225 mAh/g at1.6A/g; ~750mAh/g at 50
mA/g
G Singh/Kansas
State University[93]Automotive 2013
~99.6 % averagecoulombicefficiency); Anodeactive weight(1.0 mg/cm2),
Thickness (~125micrometers)
Electro-plated tinWashingtonState
University[88]
Consumerelectronics
2012Reduced cost. 3xcapacity vsconventional Li-ion
Solid-state platedcopper antimonidenanowire
750 Prieto battery[88]Consumerelectronics
2012
Reduced chargingtime from reducedcathode/anodegap. Increased
energy density.
Boron-doped siliconnanoparticles
1,400 mAh/g ata current rate of1 A/g, 1,000mAh/g at 2 A/g
200
University ofSouthern CaliforniaChongwu
Zhou[94]>[95]
Various 2012
Ten minutecharging time.Scalableconstruction.
Hard carbon Energ2[96]Consumerelectronics
2013greater storagecapacity
Silicon/conductingpolymer hydrogel
2,500 mAh/g to
1,100 mAh/g atcharge/dischargerate from 0.3 to3.0 A g-1.Volumetric
5,000Stanford
University[97][98]Various 2013
10x energy densityof carbon withoutdestruction caused
by 400% anode
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capacity:~1,080mAh/cm
expansion undercharge
Nanomatrix structureVolumetric: 580Wh/l
Amprius[99]`Smartphones,
providing 1850mAh capacity
2013
Uses silicon andotherelectrochemicals.Energy density
Carbon-encasedsilicon nanoparticles
2800 mAh/g atC/10
1000 at74%capacity
Stanford[100] Various 2013
Commerciallyavailable Sinanoparticlessealed insideconformal, self-supporting carbonshells, withrationally designedvoid space
between particlesand shell. Thespace allows Si
particles to expandwithout breakingthe outer carbonshell, stabilizing theSEI on the shellsurface.Coulombic
efficiency of99.84%.
Lithium/titanium/oxide Ener1/Delphi,[101] 2006durability, safety(limited density)
Fe3O4-plated coppernanorods
Universit PaulSabatier/UniversitPicardie Jules
Verne[102][103]
2006 density
Nanophosphate 2,000
A123 Systems[104]
[105][106]Automotive 2012 Operation at highand low ambient
temperature
Nickel/Tin on porousnickel
Power density:
7.4mWcm2m1
University of Illinois
at Urbana-Champaign[107][108]
Automative,electronics 2013
energy density andpower usingmicrostructuredmetal as thesubstrate for thinfilm Nickel/Tin.These areassembled asthree-dimensional
bicontinuous
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A lithium-ion battery from a laptop
computer (176 kJ)
interdigitatedmicroelectrodes.
Electrolyte
Electrolyte
Technology Durability Researchers Target application Date Benefit
Lithium imide 750-800 at 80% Leyden[88] Consumer electronics 2012 Reduced thermal expansion.
ses
i-ion batteries provide lightweight, high energy density power sources for a variety of devices. To power largerdevices, such as electric cars, connecting many small batteries in a parallel circuit is more effective [109] and moreefficient than connecting a single large battery.[citation needed] Such devices include:
Portable devices: these include mobile phones and smartphones, laptops and tablets, digital cameras and
camcorders, handheld game consoles and torches.Power tools: Li-ion batteries are used in tools such as cordless drills, sanders, saws and a variety of gardenequipment including whipper-snippers and hedge trimmers.
Electric vehicles: Because of their light weight Li-ion batteries are used for energy storage for many electricvehicles for everything from electric cars to Pedelecs, from hybrid vehicles to advanced electric wheelchairs, froradio-controlled models and model aircraft to the Mars Curiosity rover.
Though not suitable for AAA, AA, C or D form factors due to voltage per cell being more than 2 volts (i.e. 3.7 volts),hough most devices designed for a voltage that is a multiple of 1.5 can run safely on a voltage that is 30%
igher.[citation needed]
Self-discharge
i+ batteries have a self-discharge rate of approximately 510% per month,compared to over 30% per month in common nickel metal hydride batteries,approximately 1.25% per month for low self-discharge NiMH batteries and10% per month in nickel-cadmium batteries.[110]
attery life
echargeable batteries degrade with use, the capacity decreasing until it isnusably small. Li+ batteries last longer[111] if not deeply discharged
(depleted) before recharging. The smaller the depth of discharge, the longerhe battery will last.[112]
atteries may last longer if not stored fully discharged. As the battery self-discharges over time, its voltage graduallyeduces. When depleted below the low-voltage threshold of the protection circuit (2.4 to 2.9 V/cell, depending on
chemistry) it will be disabled and cannot be further discharged further until recharged.[111] It is recommended to storeatteries at 40% charge level.[111]
The rate of degradation of lithium-ion batteries is strongly temperature-dependent; they degrade much faster if stored orsed at higher temperatures. The carbon anode of the cell also generates heat. High charge levels and elevated
emperatures (whether from charging or ambient air) hasten capacity loss.[50] A test on a commonly-used LiCoO2 cellshowed that over one year a fully charged cell kept at 25 C (77 F) permanently lost 20% of total capacity; the loss
as lower when stored at lower charge levels and lower temperatures. Poor ventilation may increase temperatures,
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further shortening battery life. Loss rates vary by temperature: 6% loss at 0 C (32 F), 20% at 25 C (77 F), and5% at 40 C (104 F). When stored at 40%60% charge level, the capacity loss is reduced to 2%, 4%, and 15%,
espectively. In contrast, the calendar life of LiFePO4 cells is not affected by high charge states.[113] They may be
stored in a refrigerator.[114][115]
Charging forms deposits inside the electrolyte that inhibit ion transport. The increase in internal resistance reduces thecell's ability to deliver current. This problem is more pronounced in high-current applications. The decrease means thatolder batteries do not charge as much as new ones (charging time required decreases proportionally).
Conditioning
The need to "condition" NiCd and NiMH batteries has incorrectly leaked into folklore surrounding Li-on batteries. Theecommendation for the older technologies is to leave the device plugged in for seven or eight hours, even if fully
charged.[116] This may be a confusion of batterysoftware calibration instructions with the "conditioning" instructions foriCd and NiMH batteries.[117] The software of a typical smart phone, for example, learns how to accurately gauge the
attery's life by watching it discharge and leaving it on the charger produces a series of "micro discharges" that thesoftware can watch and learn from.
ulticell devices
i-ion batteries require a battery management system to prevent operation outside each cell's safe operating area (over-charge, under-charge, safe temperature range) and to balance cells to eliminate state of charge mismatches, therebysignificantly improving battery efficiency and increasing overall capacity.[118] As the number of cells and load currents
ncrease, the potential for mismatch increases.[119] The two kinds of mismatch are state-of-charge (SOC) andcapacity/energy ("C/E"). Though SOC is more common, each problem limits pack current capacity (mAh) to that ofhe weakest cell.
SafetySee also: Plug-in electric vehicle fire incidents and Boeing 787 Dreamliner battery problems
f overheated or overcharged, Li-ion batteries may suffer thermal runaway and cell rupture.[120] In extreme cases thiscan lead to combustion. Deep discharge may short-circuit the cell, in which case recharging would bensafe.[citation needed] To reduce these risks, lithium-ion battery packs contain fail-safe circuitry that shuts down theattery when its voltage is outside the safe range of 34.2 V per cell.[38][110] When stored for long periods the small
current draw of the protection circuitry may drain the battery below its shut down voltage; normal chargers are thenneffective. Many types of lithium-ion cell cannot be charged safely below 0 C.[121]
Other safety features are required in each cell:[38]
Shut-down separator (for overheating)Tear-away tab (for internal pressure)Vent (pressure relief)Thermal interrupt (overcurrent/overcharging)
These devices occupy useful space inside the cells, add additional points of failure and irreversibly disable the cell whenactivated. They are required because the anode produces heat during use, while the cathode may produce oxygen.These devices and improved electrode designs reduce/eliminate the risk of fire or explosion. Further, these features
ncrease costs compared to nickel metal hydride batteries, which require only a hydrogen/oxygen recombination device(preventing damage due to mild overcharging) and a back-up pressure valve.[122] Contaminants inside the cells candefeat these safety devices.
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Short-circuiting a battery will cause the cell to overheat and possibly to catch fire. Adjacent cells may then overheat andfail, possibly causing the entire battery to ignite or rupture. In the event of a fire, the device may emit dense irritatingsmoke.[123] The fire energy content (electrical + chemical) of cobalt-oxide cells is about 100 to 150 kJ per Ah, most ot chemical. Extinguishing this fire is dangerous as lithium burns violently when it comes in contact with water or moisturen the air; a suitable waterless fire extinguisher is recommended. [33][124]
eplacing the lithium cobalt oxide cathode material in lithium-ion batteries with a lithium metal phosphate such as lithiumron phosphate improves cycle counts, shelf life and safety, but lowers capacity. Currently, these 'safer' lithium-ion
atteries are mainly used in electric cars and other large-capacity battery applications, where safety is critical. [125]
ithium unlike other rechargeable batteries has a flammable electrolyte kept in pressure, because of this Li-ion batteriesave a strict quality control in manufacturing.[126] Faulty chargers can also affect the safety of the battery because they
can destroy the battery's protection circuit. While charging at temperatures below 0 C, the anode of the cells getslated with pure lithium, which can compromise the safety of the whole pack. Battery packs which are not branded by aeputable manufacturer may not be built to the same safety standard as branded ones.
n some applications the consequences of fire are particularly serious. Large lithium-ion batteries started to be used toower systems on aircraft in the 2010s; as of July 2013 there had been at least three cases of fires on the Boeing 787
assenger aircraft, introduced in 2011, which did not cause crashes but had the potential to do so[127]
.
Environmental concerns and recycling
Since Li-ion batteries contain no toxic metals (others contain lead and cadmium)[38] they are generally categorized ason-hazardous waste. Li-ion battery elements including iron, copper, nickel and cobalt are considered safe for
ncinerators and landfills. These metals can be recycled, but mining generally remains cheaper than recycling.[128] Atresent, not much is invested into recycling Li-ion batteries due to costs, complexities and low yield. The most
expensive metal involved in the construction of the cell is cobalt. Lithium iron phosphate is cheaper but has otherdrawbacks. Lithium is less expensive than other metals used. The manufacturing processes of nickel and cobalt for the
cathode and also the solvent present potential environmental and health hazards.[129][130]
ecalls
n October 2004, Kyocera Wireless recalled approximately 1 million mobile phone batteries to identify
counterfeits.[131]
n December 2006, Dell recalled approximately 22,000 laptop batteries.[132] Approximately 10 million Sony batteriessed in Dell, Sony, Apple, Lenovo, Panasonic, Toshiba, Hitachi, Fujitsu and Sharp laptops were recalled in 2006. Theatteries were found to be susceptible to internal contamination by metal particles during manufacture. Under some
circumstances, these particles could pierce the separator, causing a dangerous short-circuit.[133]
n March 2007, Lenovo recalled approximately 205,000 batteries at risk of explosion. In August 2007, Nokia recalledover 46 million batteries at risk of overheating and exploding.[134] One such incident occurred in the Philippinesnvolving a Nokia N91, which used the BL-5C battery.[135]
Transport restrictions
ATA estimates that over a billion lithium cells are flown each year. [124] In January 2008, the United States Departmentof Transportation ruled that passengers on commercial aircraft could carry lithium batteries in their checked baggage ifhe batteries were installed in a device. Types of batteries covered by this rule are those containing small amounts ofithium, including Li-ion, lithium polymer, and lithium cobalt oxide chemistries. Lithium-ion batteries containing more than5 grams (0.88 oz) equivalent lithium content (ELC) are forbidden in US air travel.[136]
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Japan Airlines Boeing 787 lithium
cobalt oxide battery that caught fire in
2013
dditionally, a limited number of replacement batteries may be transported in carry-on luggage. Such batteries must besealed in their original protective packaging or in individual containers or plastic bags. [136][137]
Some postal administrations restrict air shipping (including EMS) of lithium and lithium-ion batteries, either separately ornstalled in equipment. Such restrictions apply in Hong Kong,[138] Australia and Japan.[139]
On 16 May 2012, United States Postal Service (USPS) banned shipping anything containing a lithium battery to anoverseas address due to fires from transport of batteries.[140] Because of this
estriction, it became difficult to send anything containing lithium batteries toilitary personnel overseas, as the USPS was the only method of shipment to
hese addresses. The ban was lifted on 15 November 2012.[141]
The Boeing 787 Dreamliner contains lithium cobalt oxide[142] batteries which
are more reactive than newer types of batteries such as LiFePO4.[143]
esearch
esearchers are working to improve the power density, safety, rechargecycle, cost and other characteristics of these batteries.
Solid-state designs[144] have the potential to deliver three times the energy density of typical 2011 lithium-ion batteriesat less than half the cost per kilowatt-hour. This approach eliminates binders, separators and liquid electrolytes. Byeliminating these, "you can get around 95% of the theoretical energy density of the active materials."[145]
arlier trials of this technology encountered cost barriers, because the semiconductor industry's vacuum depositionechnology cost 2030 times too much. The new process deposits semiconductor-quality films from a solution. Theanostructured films grow directly on a substrate and then in layers on top of each other. The process allows the firm to
"spray-paint a cathode, then a separator/electrolyte, then the anode. It can be cut and stacked in various form
factors."[145]
Sandia has studied ways to improve safety and robustness of lithium ion batteries by using electrolytes such asydrofluoro ether and separators such as high-melting temperature polymers and ceramics, made via fiber spinning,
casting and vapor deposition.[146]
Tin electrodes
ashington State University researchers developed a tin anode technology that they predicted would triple the energycapacity of lithium ion batteries. The technology involves using standard electroplating process to create tin nanoneedles
hat do not shortciruit when the tin expands by one third during charging.[147][148]
icroporous tin has been used as a substrate for anode and cathodes that exhibit high energy density, power and fastecharge. The substrate self-assembles. Small spheres are packed onto a surface, forming a lattice. The area betweenhe spheres is coated with the substrate material (nickel). The spheres are dissolved/melted and the resulting surface is
electro-polished to enlarge the pores. Finally the substrate is coated with a thin film of the active material (Ni/Sn for
anode, LiMnO2 for cathode.)[67][107]
Extrusion
ARCs Hardware Systems Laboratory designed a cathode that contains more lithium by using one dense materialoptimised for storage and a second, porous one to enable speedy charge transfer. Wide storage regions alternate witharrow conductive regions. The storage region is 100 microns across, compared with ten for the conductor.[149]
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The two materials are mixed with an organic material to form pastes and fed into an additive manufacturing device thatextrudes the pastes adjacent to each other on a metal foil. Drying the substrate removes most of the organic material,eaving a solid cathode. In tests against otherwise identical batteries with monolithic cathodes, the new battery couldstore twenty percent more energy.[149]
The researchers envision extruding entire batteries using five pastestwo each for the cathode and the anode, plus a
separator.[149]
See also
Potassium-ion batteryNanowire batteryList of battery sizesList of battery types
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