Lithium iron phosphate battery

From Wikipedia, the free encyclopedia
Lithium iron phosphate battery
LiFePO4_AA
A Lithium iron phosphate (LiFePO4) AA battery (right) shown next to a battery placeholder (left)
Specific energy90–160 Wh/kg (320–580 J/g or kJ/kg)[1]
Energy density325 Wh/L (1200 kJ/L)[1]
Specific poweraround 200 W/kg[2]
Energy/consumer-price1-4 Wh/US$[3][4]
Time durability> 10 years
Cycle durability2,750–12,000[5] cycles
Nominal cell voltage3.2 V

The lithium iron phosphate battery (LiFePO
4
battery
) or LFP battery (lithium ferrophosphate) is a type of lithium-ion battery using lithium iron phosphate (LiFePO
4
) as the cathode material, and a graphitic carbon electrode with a metallic backing as the anode. Because of their low cost, high safety, low toxicity, long cycle life and other factors, LFP batteries are finding a number of roles in vehicle use, utility-scale stationary applications, and backup power.[6] LFP batteries are cobalt-free.[7] As of September 2022, LFP type battery market share for EVs reached 31%, and of that, 68% was from Tesla and Chinese EV maker BYD production alone.[8] Chinese manufacturers currently hold a near monopoly of LFP battery type production.[9] With patents having started to expire in 2022 and the increased demand for cheaper EV batteries,[10] LFP type production is expected to rise further and surpass lithium nickel manganese cobalt oxides (NMC) type batteries in 2028.[11]

The energy density of LFP batteries is lower than that of other common lithium ion battery types such as nickel manganese cobalt (NMC) and nickel cobalt aluminum (NCA). The energy density of CATL's LFP battery is currently 125 Watt-hours per kilogram (Wh/kg) and up to possibly 160 Wh/kg with improved packing technology. BYD's LFP battery energy density is 150 Wh/kg. The best NMC batteries exhibit energy densities of over 300 Wh/kg. Notably, the energy density of Panasonic’s “2170” NCA batteries used in Tesla’s 2020 Model 3 is around 260 Wh/kg, which is 70% of its "pure chemicals" value. LFP batteries also exhibit a lower operating voltage than other lithium-ion battery types.

History[edit]

LiFePO
4
is a natural mineral of the olivine family (triphylite). Arumugam Manthiram and John B. Goodenough first identified the polyanion class of cathode materials for lithium ion batteries.[12][13][14] LiFePO
4
was then identified as a cathode material belonging to the polyanion class for use in batteries in 1996 by Padhi et al.[15][16] Reversible extraction of lithium from LiFePO
4
and insertion of lithium into FePO
4
was demonstrated. Because of its low cost, non-toxicity, the natural abundance of iron, its excellent thermal stability, safety characteristics, electrochemical performance, and specific capacity (170 mA·h/g, or 610 C/g) it has gained considerable market acceptance.[17][18]

The chief barrier to commercialization was its intrinsically low electrical conductivity. This problem was overcome by reducing the particle size, coating the LiFePO
4
particles with conductive materials such as carbon nanotubes,[19][20] or both. This approach was developed by Michel Armand and his coworkers at Hydro-Québec and the Université de Montréal.[21] [22][23] Another approach by Yet Ming Chiang's group at MIT consisted of doping[17] LFP with cations of materials such as aluminium, niobium, and zirconium.

Negative electrodes (anode, on discharge) made of petroleum coke were used in early lithium-ion batteries; later types used natural or synthetic graphite.[24]

Specifications[edit]

Multiple lithium iron phosphate modules are wired in series and parallel to create a 2800 Ah 52 V battery module. Total battery capacity is 145.6 kWh. Note the large, solid tinned copper busbar connecting the modules together. This busbar is rated for 700 amps DC to accommodate the high currents generated in this 48 volt DC system.
Lithium iron phosphate modules, each 700 Ah, 3.25 V. Two modules are wired in parallel to create a single 3.25 V 1400 Ah battery pack with a capacity of 4.55 kWh.
  • Cell voltage
    • Minimum discharge voltage = 2.0-2.8 V[25][26][27]
    • Working voltage = 3.0 ~ 3.3 V
    • Maximum charge voltage = 3.60-3.65 V[28][26]
  • Volumetric energy density = 220 Wh/L (790 kJ/L)
  • Gravimetric energy density > 90 Wh/kg[29] (> 320 J/g). Up to 160 Wh/kg[1] (580 J/g).
  • Cycle life from 2,700 to more than 10,000 cycles depending on conditions.[5]

Comparison with other battery types[edit]

The LFP battery uses a lithium-ion-derived chemistry and shares many advantages and disadvantages with other lithium-ion battery chemistries. However, there are significant differences.

Resource availability[edit]

Iron and phosphates are very common in the Earth's crust. LFP contains neither nickel[30] nor cobalt, both of which are supply-constrained and expensive. As with lithium, human rights[31] and environmental[32] concerns have been raised concerning the use of cobalt. Environmental concerns have also been raised regarding the extraction of nickel.[33]

Cost[edit]

In 2020, the lowest reported LFP cell prices were $80/kWh (12.5Wh/$) with an average price of $137/kWh,[34] while in 2023 the average price had dropped to $100/kWh.[35]

A 2020 report published by the Department of Energy compared the costs of large scale energy storage systems built with LFP vs NMC. It found that the cost per kWh of LFP batteries was about 6% less than NMC, and it projected that the LFP cells would last about 67% longer (more cycles). Because of differences between the cell's characteristics, the cost of some other components of the storage system would be somewhat higher for LFP, but in balance it still remains less costly per kWh than NMC.[36]

Better aging and cycle-life characteristics[edit]

LFP chemistry offers a considerably longer cycle life than other lithium-ion chemistries. Under most conditions it supports more than 3,000 cycles, and under optimal conditions it supports more than 10,000 cycles. NMC batteries support about 1,000 to 2,300 cycles, depending on conditions.[5]

LFP cells experience a slower rate of capacity loss (a.k.a. greater calendar-life) than lithium-ion battery chemistries such as cobalt (LiCoO
2
) or manganese spinel (LiMn
2
O
4
) lithium-ion polymer batteries (LiPo battery) or lithium-ion batteries.[37]

Viable alternative to lead-acid batteries[edit]

Because of the nominal 3.2 V output, four cells can be placed in series for a nominal voltage of 12.8 V. This comes close to the nominal voltage of six-cell lead-acid batteries. Along with the good safety characteristics of LFP batteries, this makes LFP a good potential replacement for lead-acid batteries in applications such as automotive and solar applications, provided the charging systems are adapted not to damage the LFP cells through excessive charging voltages (beyond 3.6 volts DC per cell while under charge), temperature-based voltage compensation, equalisation attempts or continuous trickle charging. The LFP cells must be at least balanced initially before the pack is assembled and a protection system also needs to be implemented to ensure no cell can be discharged below a voltage of 2.5 V or severe damage will occur in most instances, due to irreversible deintercalation of LiFePO4 into FePO4.[38]

Safety[edit]

One important advantage over other lithium-ion chemistries is thermal and chemical stability, which improves battery safety.[32] LiFePO
4
is an intrinsically safer cathode material than LiCoO
2
and manganese dioxide spinels through omission of the cobalt, whose negative temperature coefficient of resistance can encourage thermal runaway. The PO bond in the (PO
4
)3−
ion is stronger than the CoO bond in the (CoO
2
)
ion, so that when abused (short-circuited, overheated, etc.), the oxygen atoms are released more slowly. This stabilization of the redox energies also promotes faster ion migration.[39]

As lithium migrates out of the cathode in a LiCoO
2
cell, the CoO
2
undergoes non-linear expansion that affects the structural integrity of the cell. The fully lithiated and unlithiated states of LiFePO
4
are structurally similar which means that LiFePO
4
cells are more structurally stable than LiCoO
2
cells.[citation needed]

No lithium remains in the cathode of a fully charged LFP cell. In a LiCoO
2
cell, approximately 50% remains. LiFePO
4
is highly resilient during oxygen loss, which typically results in an exothermic reaction in other lithium cells.[18] As a result, LiFePO
4
cells are harder to ignite in the event of mishandling (especially during charge). The LiFePO
4
battery does not decompose at high temperatures.[32]

Lower energy density[edit]

The energy density (energy/volume) of a new LFP battery is some 14% lower than that of a new LiCoO
2
battery.[40] Since discharge rate is a percentage of battery capacity, a higher rate can be achieved by using a larger battery (more ampere hours) if low-current batteries must be used.

Uses[edit]

Home energy storage[edit]

Enphase pioneered LFP along with SunFusion Energy Systems LifePO4 Ultra-Safe ECHO 2.0 and Guardian E2.0 home or business energy storage batteries for reasons of cost and fire safety, although the market remains split among competing chemistries.[41] Though lower energy density compared to other lithium chemistries adds mass and volume, both may be more tolerable in a static application. In 2021, there were several suppliers to the home end user market, including SonnenBatterie and Enphase. Tesla Motors continues to use NMC batteries in its home energy storage products, but in 2021 switched to LFP for its utility-scale battery product.[42] According to EnergySage the most frequently quoted home energy storage battery brand in the U.S. is Enphase, which in 2021 surpassed Tesla Motors and LG.[43]

Vehicles[edit]

Higher discharge rates needed for acceleration, lower weight and longer life makes this battery type ideal for forklifts, bicycles and electric cars. 12 V LiFePO4 batteries are also gaining popularity as a second (house) battery for a caravan, motor-home or boat.[44]

Tesla Motors uses LFP batteries in all standard-range Models 3 and Y made after October 2021[45] except for standard-range vehicles made with 4680 cells starting in 2022, which use an NMC chemistry.[46]

As of September 2022, LFP batteries had increased its market share of the entire EV battery market to 31%. Of those, 68% were deployed by two companies, Tesla and BYD.[47]

Lithium iron phosphate batteries officially surpassed ternary batteries in 2021 with 52% of installed capacity. Analysts estimate that its market share will exceed 60% in 2024.[48]

In February 2023, Ford announced that it will be investing $3.5 billion to build a factory in Michigan that will produce low-cost batteries for some of its electric vehicles. The project will be fully owned by a Ford subsidiary, but will use technology licensed from Chinese battery company Contemporary Amperex Technology Co., Limited (CATL).[49]

Solar-powered lighting systems[edit]

Single "14500" (AA battery–sized) LFP cells are now used in some solar-powered landscape lighting instead of 1.2 V NiCd/NiMH.[citation needed]

LFP's higher[clarification needed] (3.2 V) working voltage lets a single cell drive an LED without circuitry to step up the voltage. Its increased tolerance to modest overcharging (compared to other Li cell types) means that LiFePO
4
can be connected to photovoltaic cells without circuitry to halt the recharge cycle.

By 2013, better solar-charged passive infrared motion detector security lamps emerged.[50] As AA-sized LFP cells have a capacity of only 600 mAh (while the lamp's bright LED may draw 60 mA), the units shine for at most 10 hours. However, if triggering is only occasional, such units may be satisfactory even charging in low sunlight, as lamp electronics ensure after-dark "idle" currents of under 1 mA.[citation needed]

Other uses[edit]

Some electronic cigarettes use these types of batteries. Other applications include marine electrical systems[51] and propulsion, flashlights, radio-controlled models, portable motor-driven equipment, amateur radio equipment, industrial sensor systems[52] and emergency lighting.[53]

A recent modification discussed here [54] is to replace the potentially unstable separator with a more stable material. Recent discoveries found that LiFePO4 and to an extent Li-ion can degrade due to heat, when test cells were taken apart a brick red compound had formed that when analyzed suggesting that molecular breakdown of the previously believed stable separator was a common failure mode. In this case, the side reactions gradually consume Li ions trapping them in stable compounds so they can't be shuttled. Also three electrode batteries that permit external devices to detect internal shorts forming are a potential near term solution to the dendrite issue.

See also[edit]

References[edit]

  1. ^ a b c "Great Power Group, Square lithium-ion cell". Archived from the original on 2020-08-03. Retrieved 2019-12-31.
  2. ^ "12,8 Volt Lithium-Iron-Phosphate Batteries" (PDF). VictronEnergy.nl. Archived from the original (PDF) on 2016-09-21. Retrieved 2016-04-20.
  3. ^ "Zooms 12V 100Ah LiFePO4 Deep Cycle Battery, Rechargeable Lithium Iron Phosphate Battery". Amazon.com. Archived from the original on 2022-01-25. Retrieved 2022-01-25.
  4. ^ "ZEUS Battery Products - 12.8 V Lithium Iron Phosphate Battery Rechargeable (Secondary) 20Ah". DigiKey.com. Archived from the original on 2022-01-25. Retrieved 2022-01-25.
  5. ^ a b c Preger, Yuliya; Barkholtz, Heather M.; Fresquez, Armando; Campbell, Daniel L.; Juba, Benjamin W.; Romàn-Kustas, Jessica; Ferreira, Summer R.; Chalamala, Babu (2020). "Degradation of Commercial Lithium-Ion Cells as a Function of Chemistry and Cycling Conditions". Journal of the Electrochemical Society. Institute of Physics. 167 (12): 120532. Bibcode:2020JElS..167l0532P. doi:10.1149/1945-7111/abae37. S2CID 225506214.
  6. ^ Learn about lithium batteries ethospower.org
  7. ^ Li, Wangda; Lee, Steven; Manthiram, Arumugam (2020). "High-Nickel NMA: A Cobalt-Free Alternative to NMC and NCA Cathodes for Lithium-Ion Batteries". Advanced Materials. 32 (33): e2002718. Bibcode:2020AdM....3202718L. doi:10.1002/adma.202002718. PMID 32627875.
  8. ^ "Tesla, BYD accounted for 68% of LFP batteries deployed from Q1-Q3 2022". 15 December 2022.
  9. ^ "Japan battery material producers lose spark as China races ahead".
  10. ^ "A Handful of Lithium Battery Patents Are Set to Expire Before the End of the Year, Hopefully Bringing EV Prices Down With Them | GetJerry.com". getjerry.com. Retrieved 2023-04-12.
  11. ^ "Global lithium-ion battery capacity to rise five-fold by 2030". 22 March 2022.
  12. ^ Masquelier, Christian; Croguennec, Laurence (2013). "Polyanionic (Phosphates, Silicates, Sulfates) Frameworks as Electrode Materials for Rechargeable Li (or Na) Batteries". Chemical Reviews. 113 (8): 6552–6591. doi:10.1021/cr3001862. PMID 23742145.
  13. ^ Manthiram, A.; Goodenough, J. B. (1989). "Lithium insertion into Fe2(SO4)3 frameworks". Journal of Power Sources. 26 (3–4): 403–408. Bibcode:1989JPS....26..403M. doi:10.1016/0378-7753(89)80153-3.
  14. ^ Manthiram, A.; Goodenough, J. B. (1987). "Lithium insertion into Fe2(MO4)3 frameworks: Comparison of M = W with M = Mo". Journal of Solid State Chemistry. 71 (2): 349–360. Bibcode:1987JSSCh..71..349M. doi:10.1016/0022-4596(87)90242-8.
  15. ^ "LiFePO
    4
    : A Novel Cathode Material for Rechargeable Batteries", A.K. Padhi, K.S. Nanjundaswamy, J.B. Goodenough, Electrochemical Society Meeting Abstracts, 96-1, May, 1996, pp 73
  16. ^ "Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries" A. K. Padhi, K. S. Nanjundaswamy, and J. B. Goodenough, J. Electrochem. Soc., Volume 144, Issue 4, pp. 1188-1194 (April 1997)
  17. ^ a b Gorman, Jessica (September 28, 2002). "Bigger, Cheaper, Safer Batteries: New material charges up lithium-ion battery work". Science News. Vol. 162, no. 13. p. 196. Archived from the original on 2008-04-13.
  18. ^ a b "Building safer Li ion batteries". houseofbatteries.com. Archived from the original on 2011-01-31.
  19. ^ Susantyoko, Rahmat Agung; Karam, Zainab; Alkhoori, Sara; Mustafa, Ibrahim; Wu, Chieh-Han; Almheiri, Saif (2017). "A surface-engineered tape-casting fabrication technique toward the commercialisation of freestanding carbon nanotube sheets". Journal of Materials Chemistry A. 5 (36): 19255–19266. doi:10.1039/c7ta04999d. ISSN 2050-7488.
  20. ^ Susantyoko, Rahmat Agung; Alkindi, Tawaddod Saif; Kanagaraj, Amarsingh Bhabu; An, Boohyun; Alshibli, Hamda; Choi, Daniel; AlDahmani, Sultan; Fadaq, Hamed; Almheiri, Saif (2018). "Performance optimization of freestanding MWCNT-LiFePO4 sheets as cathodes for improved specific capacity of lithium-ion batteries". RSC Advances. 8 (30): 16566–16573. Bibcode:2018RSCAd...816566S. doi:10.1039/c8ra01461b. ISSN 2046-2069. PMC 9081850. PMID 35540508.
  21. ^ US 20150132660A1, Ravet, N.; Simoneau, M. & Armand, M. et al., "Electrode materials with high surface conductivity", published 2015/05/14, assigned to Hydro-Québec 
  22. ^ Armand, Michel; Goodenough, John B.; Padhi, Akshaya K.; Nanjundaswam, Kirakodu S.; Masquelier, Christian (Feb 4, 2003), Cathode materials for secondary (rechargeable) lithium batteries, archived from the original on 2016-04-02, retrieved 2016-02-25
  23. ^ Long Hard Road: The Lithium-Ion Battery and the Electric Car. 2022. C.J. Murray. ISBN 978-1-61249-762-4
  24. ^ David Linden (ed.), Handbook of Batteries 3rd Edition,McGraw Hill 2002, ISBN 0-07-135978-8, pages 35-16 and 35-17
  25. ^ "Cell — CA Series". CALB.cn. Archived from the original on 2014-10-09.
  26. ^ a b "A123 Systems ANR26650". 2022-07-30.
  27. ^ "LiFePO4 Battery". 2022-07-30.
  28. ^ "LiFePO4 Battery". www.evlithium.com. Retrieved 2020-09-24.
  29. ^ "Large-Format, Lithium Iron Phosphate". JCWinnie.biz. 2008-02-23. Archived from the original on 2008-11-18. Retrieved 2012-04-24.
  30. ^ "Nickel battery infographic" (PDF).
  31. ^ "Transition Minerals Tracker" (PDF). humanrights.org.
  32. ^ a b c Rechargeable Lithium Batteries. Archived from the original on 2011-07-14. {{cite encyclopedia}}: |work= ignored (help)
  33. ^ "'We are afraid': Erin Brockovich pollutant linked to global electric car boom". the Guardian. 2022-02-19. Retrieved 2022-02-19.
  34. ^ "Battery Pack Prices Cited Below $100/kWh for the First Time in 2020, While Market Average Sits at $137/kWh". December 16, 2020.
  35. ^ Colthorpe, Andy (27 November 2023). "LFP cell average falls below US$100/kWh as battery pack prices drop to record low in 2023". Energy-Storage.News.
  36. ^ Mongird, Kendall; Viswanatha, Vilayanur (December 2020). 2020 Grid Energy Storage Technology Cost and Performance Assessment (pdf) (Technical report). U.S. Department of Energy. DOE/PA-0204.{{cite tech report}}: CS1 maint: date and year (link)
  37. ^ "ANR26650M1". A123Systems. 2006. Archived from the original on 2012-03-01. Current test projecting excellent calendar life: 17% impedance growth and 23% capacity loss in 15 years at 100% SOC, 60°C.
  38. ^ Inoue, Katsuya; Fujieda, Shun; Shinoda, Kozo; Suzuki, Shigeru; Waseda, Yoshio (2010). "Chemical State of Iron of LiFePO4 during Charge-Discharge Cycles Studied by In-Situ X-ray Absorption Spectroscopy". Materials Transactions. 51 (12): 2220–2224. doi:10.2320/matertrans.M2010229. ISSN 1345-9678.
  39. ^ "Lithium Ion batteries | Lithium Polymer | Lithium Iron Phosphate". Harding Energy. Archived from the original on 2016-03-29. Retrieved 2016-04-06.
  40. ^ Guo, Yu-Guo; Hu, Jin-Song; Wan, Li-Jun (2008). "Nanostructured Materials for Electrochemical Energy Conversion and Storage Devices". Advanced Materials. 20 (15): 2878–2887. Bibcode:2008AdM....20.2878G. doi:10.1002/adma.200800627.
  41. ^ "Enphase Energy Enters into Energy Storage Business with AC Battery | Enphase Energy". newsroom.enphase.com.
  42. ^ "Tesla's Shift to LFP Batteries: What to Know | EnergySage". August 12, 2021.
  43. ^ "Latest EnergySage marketplace report shows quoted battery prices are rising". Solar Power World. August 16, 2021.
  44. ^ "Lithium Iron Phosphate Battery". Lithium Storage.
  45. ^ Gitlin, Jonathan M. (October 21, 2021). "Tesla made $1.6 billion in Q3, is switching to LFP batteries globally". Ars Technica.
  46. ^ Tesla 4680 Teardown: Specs Revealed! (Part 2), retrieved 2023-05-15
  47. ^ "EV Battery Market: LFP Chemistry Reached 31% Share In September". MSN. Retrieved 2023-04-12.
  48. ^ "EV Lithium Iron Phosphate Battery Battles Back". energytrend.com. 2022-05-25.
  49. ^ "Ford to build $3.5 billion electric vehicle battery plant in Michigan". CBS News. February 13, 2023. Archived from the original on February 14, 2023.
  50. ^ "instructables.com". Archived from the original on 2014-04-16. Retrieved 2014-04-16.
  51. ^ "Why Fisherman Are Switching to Lithium Batteries". Astro Lithium. Retrieved 2023-03-29.
  52. ^ "IECEx System". iecex.iec.ch. Archived from the original on 2018-08-27. Retrieved 2018-08-26.
  53. ^ "EM ready2apply BASIC 1 – 2 W". Tridonic. Retrieved 23 October 2018.
  54. ^ Liu, Zhifang; Jiang, Yingjun; Hu, Qiaomei; Guo, Songtao; Yu, Le; Li, Qi; Liu, Qing; Hu, Xianluo (2021). "Safer Lithium‐Ion Batteries from the Separator Aspect: Development and Future Perspectives". Energy & Environmental Materials. 4 (3): 336–362. doi:10.1002/eem2.12129. S2CID 225241307.