Chemistry:Lithium nickel cobalt aluminium oxides

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The lithium nickel cobalt aluminium oxides (abbreviated as Li-NCA, LNCA, or NCA) are a group of mixed metal oxides. Some of them are important due to their application in lithium ion batteries. NCAs are used as active material in the positive electrode (which is the cathode when the battery is discharged). NCAs are composed of the cations of the chemical elements lithium, nickel, cobalt and aluminium. The compounds of this class have a general formula LiNixCoyAlzO2 with x + y + z = 1. In case of the NCA comprising batteries currently available on the market, which are also used in electric cars and electric appliances, x ≈ 0,8, and the voltage of those batteries is between 3.6 V and 4.0 V, at a nominal voltage of 3.6 V or 3.7 V. A version of the oxides currently in use in 2019 is LiNi0,84Co0,12Al0,04O2.


Properties of NCA

The usable charge storage capacity of NCA is about 180 to 200 mAh/g.[1] This is well below the theoretical values; for LiNi0,8Co0,15Al0,05O2 this is 279 mAh/g.[2] However, the capacity of NCA is significantly higher than that of alternative materials such as lithium cobalt oxide LiCoO2 with 148 mAh/g, lithium iron phosphate LiFePO4 with 165 mAh/g and NMC 333 LiNi0,33Mn0,33Co0,33O2 with 170 mAh/g.[2] Like LiCoO2 and NMC, NCA belongs to the cathode materials with layer structure.[1] Due to the high voltage, NCA enables batteries with high energy density. Another advantage of NCA is its excellent fast charging capability.[1] Disadvantages are the high costs and the limited resources of cobalt and nickel.[1]

The two materials NCA and NMC have related structures, quite similar electrochemical behaviour and show similar performance, in particular relatively high energy densities and relatively high performance. Noteworthy, Ni is cycled during the battery operation between oxidation states +2 and +3.5, Co- between +2 and +3, and Mn and Al remain electrochemically inactive.[3]

It is estimated that the NCA battery pack Tesla Model 3 contains between 4.5 and 9.5 kg of cobalt and 11.6 kg of lithium.[4]

Kristallstruktur von Nickel(IV)-oxid

Lithium nickel oxide LiNiO2, which is closely related to NCA, or nickel oxide NiO2 itself, cannot yet be used as a battery material because it is mechanically unstable, shows a rapid loss of capacity and has safety issues.[5]

Nickel-rich NCA: advantages and limitations

NCAs LiNixCoyAlzO2 with x ≥ 0.8 are called nickel rich;[6] those compounds are the most important variants of the substance class. The nickel-rich variants are also low in cobalt and therefore have a cost advantage, as cobalt is several times more expensive than nickel. Furthermore, as the nickel content increases, so does the voltage and the mAh/g charge that can be stored in the battery. This is because Co is cycled in a battery between oxidation states +3 and +3.5 (i.e. with 0.5 electron/cobalt atom), while nickel can go between +3 and +4 (i.e. 1 electron/nickel atom). Thus, increasing the molar fraction of nickel in the posode increases both the mAh/g number and the cell voltage. However, as the nickel content increases, the risk of thermal breakdown and premature aging of the battery also increases. When a typical NCA battery is heated to 180 °C, it will thermally run away.[7] If the battery was previously overcharged, thermal run away can occur even at 65 °C.[7] The aluminium ions in NCA increase stability and safety, but they reduce capacity because they do not participate in oxidation and reduction themselves.

Modifications of the material

To make NCA more resistant, in particular for batteries that need to operate at temperatures above 50 °C, the NCA active material is usually coated. The coatings demonstrated in research may comprise fluorides such as aluminium fluoride AlF3, crystalline oxides (e.g. CoO2, TiO2, NMC) or glassy oxides (silicon dioxide SiO2) or phosphates such as FePO4.[2]

NCA batteries: Manufacturers and use

The main producers of NCA and their market shares in 2015 were Sumitomo Metal Mining with 58%, Toda Kogyo (BASF) with 16%, Nihon Kagaku Sangyo with 13% and Ecopro with 5%.[8] Sumitomo supplies Tesla and Panasonic and was able to produce 850 tons of NCA per month in 2014.[9] In 2016, Sumitomo increased its monthly production capacity to 2550 tons,[10] and in 2018 to 4550 tons.[9] In China, in Tongren County in Qinghai Province, a plant has been under construction since 2019, which will initially produce 1500 tons of NCA per month.[11]

As of 2018, the most important manufacturer of NCA batteries was reportedly Panasonic, or Panasonic's cooperation partner Tesla,[2] as Tesla uses NCA as active material in the traction batteries of its car models.[12][13] In Tesla Model 3[5] and Tesla Model X, LiNi0,84Co0,12Al0,04O2 is used.[14] With a few exceptions, current electric cars as of 2019 use either NCA or alternatively lithium nickel manganese cobalt oxides (NMC).[5] In addition to use in electric cars, NCA is also used in batteries for electronic devices, mainly by Panasonic, Sony and Samsung.[8] Some cordless vacuum cleaners are also equipped with NCA batteries.[15][better source needed]

References

  1. ↑ 1.0 1.1 1.2 1.3 Marca M. Doeff (2013), Ralph J. Brodd, ed., "Battery Cathodes: Selected Entries from the Encyclopedia of Sustainability Science and Technology", Batteries for Sustainability (New York, NY: Springer): 5–49, doi:10.1007/978-1-4614-5791-6_2, ISBN 978-1-4614-5790-9 
  2. ↑ 2.0 2.1 2.2 2.3 Agus Purwanto; Cornelius Satria Yudha; U Ubaidillah; Hendri Widiyandari; Takashi Ogi (2018-09-26), "NCA cathode material: synthesis methods and performance enhancement efforts", Materials Research Express (IOP Publishing) 5 (12): 122001, doi:10.1088/2053-1591/aae167, ISSN 2053-1591, Bibcode: 2018MRE.....5l2001P 
  3. ↑ A reflection on lithium-ion battery cathode chemistry. 2020. Nature Communications. 11/1, 9. A. Manthiram. doi: 10.1038/s41467-020-15355-0.
  4. ↑ Evan Leon (2018-10-26). "From Mine to Market: Energy Metals & Electric Vehicle Industrialization" (in en). University of Michigan Energy Institute. https://energy.umich.edu/te3/wp-content/uploads/sites/2/2018/11/Evan-Leon.pdf. 
  5. ↑ 5.0 5.1 5.2 Matteo Bianchini; Maria Roca-Ayats; Pascal Hartmann; Torsten Brezesinski; Jürgen Janek (2019-07-29), "There and Back Again-The Journey of LiNiO2 as a Cathode Active Material", Angewandte Chemie International Edition (Wiley-VCH) 58 (31): 10434–10458, doi:10.1002/anie.201812472, PMID 30537189, https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201812472, retrieved 2021-11-26 
  6. ↑ Sheng S. Zhang (January 2020), "Problems and their origins of Ni-rich layered oxide cathode materials", Energy Storage Materials 24: pp. 247–254, https://www.sciencedirect.com/science/article/abs/pii/S2405829719309262, retrieved 2021-11-26 
  7. ↑ 7.0 7.1 Xuan Liu; Kang Li; Xiang Li (2018). "The Electrochemical Performance and Applications of Several Popular Lithium-ion Batteries for Electric Vehicles - A Review". in K. Li. ICSEE 2018, IMIOT 2018. 925. Springer, Singapore. pp. 201–213. doi:10.1007/978-981-13-2381-2_19. ISBN 9789811323805. https://link.springer.com/chapter/10.1007%2F978-981-13-2381-2_19. Retrieved 2021-11-26.  See also this alternative academic article source.
  8. ↑ 8.0 8.1 Christophe Pillot (2017-01-30). "Lithium ion battery raw material Supply & demand 2016–2025" (in en). Avicenne. http://www.avicenne.com/pdf/Lithium-Ion%20Battery%20Raw%20Material%20Supply%20and%20Demand%202016-2025%20C.%20Pillot%20-%20M.%20Sanders%20Presentation%20at%20AABC-US%20San%20Francisco%20June%202017.pdf. 
  9. ↑ 9.0 9.1 Yuka Obayashi, Ritsuko Shimizu (2018-09-13). "Japan's Sumitomo to focus on battery material supply to Panasonic, Toyota". https://www.reuters.com/article/us-sumitomo-mtl-min-strategy-idUSKCN1LT1SN. 
  10. ↑ James Ayre (2016-02-26). "Sumitomo Metal Mining Boosting NCA (Used In Lithium-Ion Cathodes) Production By 38 %, In Anticipation Of Tesla Model 3 Launch" (in en). https://evobsession.com/sumitomo-metal-thumbng-boosting-nca-used-in-lithium-ion-cathodes-production-by-38-in-anticipation-of-tesla-model-3-launch/. 
  11. ↑ Frank Liu (2019-11-13). "Construction of 50,000 mt NCA cathode material project began in Qinghai" (in en). Shanghai Metals Market SMM, SMM Information & Technology Co. https://news.metal.com/newscontent/100992826/Construction-of-50,000-mt-NCA-cathode-material-project-began-in-Qinghai/. 
  12. ↑ James Ayre (2017-12-02). "Tesla Batteries 101 — Production Capacity, Uses, Chemistry, & Future Plans" (in en-US). https://cleantechnica.com/2017/12/02/tesla-batteries-101-production-capacity-uses-chemistry-future-plans/. 
  13. ↑ Fred Lambert (2017-05-04). "Tesla battery researcher unveils new chemistry to increase lifecycle at high voltage" (in en-US). Electrek, 9to5 network. https://electrek.co/2017/05/04/tesla-battery-researcher-chemistry-lifcycle/. 
  14. ↑ Gyeong Won Nam; Nam-Yung Park; Kang-Joon Park; Jihui Yang; Jun Liu (2019-12-13), "Capacity Fading of Ni-Rich NCA Cathodes: Effect of Microcracking Extent", ACS Energy Letters 4 (12): 2995–3001, doi:10.1021/acsenergylett.9b02302, ISSN 2380-8195, https://pubs.acs.org/doi/full/10.1021/acsenergylett.9b02302, retrieved 2021-11-26 
  15. ↑ Cite error: Invalid <ref> tag; no text was provided for refs named powertoollab

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