Chemistry:Lithium iron phosphate battery

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Short description: Type of rechargeable battery
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 (LiFePO4 battery) or LFP battery (lithium ferrophosphate) is a type of lithium-ion battery using lithium iron phosphate (LiFePO4) 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

Main page: Chemistry:Lithium iron phosphate

LiFePO4 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] LiFePO4 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 LiFePO4 and insertion of lithium into FePO4 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 LiFePO4 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

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

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

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

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

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 (LiCoO2) or manganese spinel (LiMn2O4) lithium-ion polymer batteries (LiPo battery) or lithium-ion batteries.[37]

Viable alternative to lead-acid batteries

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

One important advantage over other lithium-ion chemistries is thermal and chemical stability, which improves battery safety.[32] LiFePO4 is an intrinsically safer cathode material than LiCoO2 and manganese dioxide spinels through omission of the cobalt, whose negative temperature coefficient of resistance can encourage thermal runaway. The P–O bond in the (PO4)3− ion is stronger than the Co–O bond in the (CoO2)− 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 LiCoO2 cell, the CoO2 undergoes non-linear expansion that affects the structural integrity of the cell. The fully lithiated and unlithiated states of LiFePO4 are structurally similar which means that LiFePO4 cells are more structurally stable than LiCoO2 cells.[citation needed]

No lithium remains in the cathode of a fully charged LFP cell. In a LiCoO2 cell, approximately 50% remains. LiFePO4 is highly resilient during oxygen loss, which typically results in an exothermic reaction in other lithium cells.[18] As a result, LiFePO4 cells are harder to ignite in the event of mishandling (especially during charge). The LiFePO4 battery does not decompose at high temperatures.[32]

Lower energy density

The energy density (energy/volume) of a new LFP battery is some 14% lower than that of a new LiCoO2 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

Home energy storage

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

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

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 (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 LiFePO4 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

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


References

  1. ↑ 1.0 1.1 1.2 "Great Power Group, Square lithium-ion cell". http://www.greatpower.net/cplb/info_159.aspx?itemid=292&cid=25. 
  2. ↑ "12,8 Volt Lithium-Iron-Phosphate Batteries". https://www.victronenergy.nl/upload/documents/Datasheet-12,8-Volt-lithium-iron-phosphate-batteries-EN.pdf. 
  3. ↑ "Zooms 12V 100Ah LiFePO4 Deep Cycle Battery, Rechargeable Lithium Iron Phosphate Battery". https://www.amazon.com/dp/B094NN5KWY/ref=cm_sw_r_apan_glt_i_BKJA8YA3Z4ZV2A9BKZ09. 
  4. ↑ "ZEUS Battery Products - 12.8 V Lithium Iron Phosphate Battery Rechargeable (Secondary) 20Ah". https://www.digikey.com/en/products/detail/zeus-battery-products/PCLFP20-12.8M6/9828821. 
  5. ↑ 5.0 5.1 5.2 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. doi:10.1149/1945-7111/abae37. Bibcode: 2020JElS..167l0532P. 
  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. doi:10.1002/adma.202002718. PMID 32627875. Bibcode: 2020AdM....3202718L. 
  8. ↑ "Tesla, BYD accounted for 68% of LFP batteries deployed from Q1-Q3 2022". 15 December 2022. https://www.teslarati.com/tesla-byd-68-percent-all-lfp-batteries-deployed-q1-q3-2022-report/. 
  9. ↑ "Japan battery material producers lose spark as China races ahead". https://asia.nikkei.com/Business/Materials/Japan-battery-material-producers-lose-spark-as-China-races-ahead2#selection-2549.353-2557.282. 
  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" (in en). https://getjerry.com/electric-vehicles/lithium-batttery-patents-expire-before-end-of-year. 
  11. ↑ "Global lithium-ion battery capacity to rise five-fold by 2030". 22 March 2022. https://www.woodmac.com/press-releases/global-lithium-ion-battery-capacity-to-rise-five-fold-by-2030/. 
  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. doi:10.1016/0378-7753(89)80153-3. Bibcode: 1989JPS....26..403M. 
  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. doi:10.1016/0022-4596(87)90242-8. Bibcode: 1987JSSCh..71..349M. 
  15. ↑ "LiFePO4: 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. ↑ 17.0 17.1 Gorman, Jessica (September 28, 2002). "Bigger, Cheaper, Safer Batteries: New material charges up lithium-ion battery work". Science News 162 (13): 196. http://www.sciencenews.org/articles/20020928/fob4.asp. 
  18. ↑ 18.0 18.1 "Building safer Li ion batteries". houseofbatteries.com. http://www.houseofbatteries.com/articles.php?id=27. 
  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" (in en). 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 et al. (2018). "Performance optimization of freestanding MWCNT-LiFePO4 sheets as cathodes for improved specific capacity of lithium-ion batteries" (in en). RSC Advances 8 (30): 16566–16573. doi:10.1039/c8ra01461b. ISSN 2046-2069. PMID 35540508. Bibcode: 2018RSCAd...816566S. 
  21. ↑ Ravet, N.; Simoneau, M. & Armand, M. et al., "Electrode materials with high surface conductivity", US patent 20150132660A1, 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, http://www.google.com/patents/US6514640, 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". http://en.calb.cn/product/?id-116.html. 
  26. ↑ 26.0 26.1 "A123 Systems ANR26650". 2022-07-30. https://a123batteries.com/anr26650m1-b-lithiumwerks-nanophosphate-3-3v-2-5ah-lithium-iron-phosphate-battery/. 
  27. ↑ "LiFePO4 Battery". 2022-07-30. http://www.evlithium.com/LiFePO4-Battery/. 
  28. ↑ "LiFePO4 Battery". http://www.evlithium.com/LiFePO4-Battery/. 
  29. ↑ "Large-Format, Lithium Iron Phosphate". JCWinnie.biz. 2008-02-23. http://jcwinnie.biz/wordpress/?p=2823. 
  30. ↑ "Nickel battery infographic". https://www.nickelinstitute.org/media/1987/nickel_battery_infographic-final2.pdf. 
  31. ↑ "Transition Minerals Tracker". https://media.business-humanrights.org/media/documents/files/Transition_Minerals_Tracker_-_Overall_v2.pdf. 
  32. ↑ 32.0 32.1 32.2 "Rechargeable Lithium Batteries". Rechargeable Lithium Batteries. http://www.mpoweruk.com/lithiumS.htm. 
  33. ↑ "'We are afraid': Erin Brockovich pollutant linked to global electric car boom" (in en). 2022-02-19. https://www.theguardian.com/global-development/2022/feb/19/we-are-afraid-erin-brockovich-pollutant-linked-to-global-electric-car-boom. 
  34. ↑ "Battery Pack Prices Cited Below $100/kWh for the First Time in 2020, While Market Average Sits at $137/kWh". December 16, 2020. https://about.bnef.com/blog/battery-pack-prices-cited-below-100-kwh-for-the-first-time-in-2020-while-market-average-sits-at-137-kwh/. 
  35. ↑ Colthorpe, Andy (27 November 2023). "LFP cell average falls below US$100/kWh as battery pack prices drop to record low in 2023". https://www.energy-storage.news/lfp-cell-average-falls-below-us100-kwh-as-battery-pack-prices-drop-to-record-low-in-2023/. 
  36. ↑ Template:Cite tech report
  37. ↑ "ANR26650M1". A123Systems. 2006. http://www.rc-netbutik.dk/getdoc.asp?id=100&md5hash=9810C237586CF6B4325753101E37DAE1. "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" (in en). Materials Transactions 51 (12): 2220–2224. doi:10.2320/matertrans.M2010229. ISSN 1345-9678. https://www.jstage.jst.go.jp/article/matertrans/51/12/51_M2010229/_article. 
  39. ↑ "Lithium Ion batteries | Lithium Polymer | Lithium Iron Phosphate" (in en-US). http://www.hardingenergy.com/lithium/#phosphate. 
  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. doi:10.1002/adma.200800627. Bibcode: 2008AdM....20.2878G. 
  41. ↑ "Enphase Energy Enters into Energy Storage Business with AC Battery | Enphase Energy". https://newsroom.enphase.com/news-releases/news-release-details/enphase-energy-enters-energy-storage-business-ac-battery/. 
  42. ↑ "Tesla's Shift to LFP Batteries: What to Know | EnergySage". August 12, 2021. https://52.4.25.117/teslas-shift-to-lfp-batteries/. 
  43. ↑ "Latest EnergySage marketplace report shows quoted battery prices are rising". August 16, 2021. https://www.solarpowerworldonline.com/2021/08/latest-energysage-marketplace-report-shows-quoted-battery-prices-are-rising/. 
  44. ↑ "Lithium Iron Phosphate Battery". https://www.lithiumstoragebattery.com/products/lithium-iron-phosphate-battery.html. 
  45. ↑ Gitlin, Jonathan M. (October 21, 2021). "Tesla made $1.6 billion in Q3, is switching to LFP batteries globally". https://arstechnica.com/cars/2021/10/tesla-made-1-6-billion-in-q3-is-switching-to-lfp-batteries-globally/. 
  46. ↑ (in en) Tesla 4680 Teardown: Specs Revealed! (Part 2), https://www.youtube.com/watch?v=8WPPBhqeekw, retrieved 2023-05-15 
  47. ↑ "EV Battery Market: LFP Chemistry Reached 31% Share In September" (in en-MY). https://www.msn.com/en-my/news/other/ev-battery-market-lfp-chemistry-reached-31percent-share-in-september/ar-AA15GAoQ. 
  48. ↑ "EV Lithium Iron Phosphate Battery Battles Back". 2022-05-25. https://m.energytrend.com/news/20220520-28100.html. 
  49. ↑ "Ford to build $3.5 billion electric vehicle battery plant in Michigan". CBS News. February 13, 2023. https://www.cbsnews.com/news/ford-to-build-3-5b-electric-vehicle-battery-plant-in-mich/#:~:text=plans%20to%20build%20a%20%243.5,start%20making%20batteries%20in%202026.. 
  50. ↑ "instructables.com". http://www.instructables.com/file/FTWJQ1LHTVDZNRW. 
  51. ↑ "Why Fisherman Are Switching to Lithium Batteries" (in en). https://astrolithium.com/blogs/news/why-fisherman-are-switching-to-lithium-batteries. 
  52. ↑ "IECEx System" (in en). http://iecex.iec.ch/iecex/exs.nsf/ex_eq.xsp?v=e. 
  53. ↑ "EM ready2apply BASIC 1 – 2 W" (in en). Tridonic. https://www.tridonic.com/com/en/products/em-ready2apply-basic-1-2w.asp. 
  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. 

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