Lithium nickel cobalt aluminium oxides

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The lithium nickel cobalt aluminium oxides (NCA) are a group of substances comprising metal oxides. Some of them are important due to their application in lithium ion batteries. NCAs are used as active material on the positive pole (which is the cathode when the battery is discharged). NCAs are mixed oxides comprising the cations of the chemical elements lithium, nickel, cobalt and aluminium. The most important representatives have the 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.

NCA batteries: Manufacturer and use[]

The most important manufacturer of NCA batteries is Panasonic or Panasonic's cooperation partner Tesla,[1] as Tesla uses NCA as active material in the traction batteries of its car models.[2][3] In Tesla Model 3[4] and Tesla Model X, LiNi0,84Co0,12Al0,04O2 is used.[5] With a few exceptions, current electric cars as of 2019 use either NCA or alternatively lithium nickel manganese cobalt oxides (NMC).[4] In addition to use in electric cars, NCA is also used in batteries for electronic devices, mainly by Panasonic, Sony and Samsung.[6] are also equipped with NCA batteries.[7]

Manufacturer of NCA[]

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%.[6] Sumitomo supplies Tesla and Panasonic and was able to produce 850 tons of NCA per month in 2014.[8] In 2016, Sumitomo increased its monthly production capacity to 2550 tons,[9] and in 2018 to 4550 tons.[8] 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.[10]

Properties of NCA[]

The usable charge storage capacity of NCA is about 180 to 200 mAh/g.[11] This is well below the theoretical values; for LiNi0,8Co0,15Al0,05O2 this is 279 mAh/g.[1] 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.[1] Like LiCoO2 and NMC, NCA belongs to the cathode materials with layer structure.[11] Due to the high voltage, NCA enables batteries with high energy density. Another advantage of NCA is its excellent fast charging capability.[11] Disadvantages are the high costs and the limited resources of cobalt and nickel.[11]

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. It is estimated that the NCA battery of Model 3 contains between 4.5 and 9.5 kg of cobalt and 11.6 kg of lithium.[12]

Kristallstruktur von Nickel(IV)-oxid

LiNiO2, which is closely related to NCA, or nickel oxide NiO2 itself, cannot yet be used as a battery material because they are mechanically unstable, shows a rapid loss of capacity and have safety issues.[4]

Nickel-rich NCA: advantages and limitations[]

NCAs LiNixCoyAlzO2 with x ≥ 0.8 are called nickel rich;[13] 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 relatively expensive. Furthermore, as the nickel content increases, so does the voltage and thus the energy that can be stored in the battery. 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.[14] If the battery was previously overcharged, thermal run away can occur even at 65 °C.[14] 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.[1]

References[]

  1. ^ Jump up to: a b c d 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), p. 122001, doi:10.1088/2053-1591/aae167, ISSN 2053-1591CS1 maint: multiple names: authors list (link)
  2. ^ James Ayre (2017-12-02). "Tesla Batteries 101 — Production Capacity, Uses, Chemistry, & Future Plans". CleanTechnica.
  3. ^ Fred Lambert (2017-05-04). "Tesla battery researcher unveils new chemistry to increase lifecycle at high voltage". Electrek. Electrek, 9to5 network.
  4. ^ Jump up to: a b c 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), pp. 10434–10458, doi:10.1002/anie.201812472CS1 maint: multiple names: authors list (link)
  5. ^ 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), pp. 2995–3001, doi:10.1021/acsenergylett.9b02302, ISSN 2380-8195CS1 maint: multiple names: authors list (link)
  6. ^ Jump up to: a b Christophe Pillot (2017-01-30). "Lithium ion battery raw material Supply & demand 2016–2025" (PDF). avicenne.com. Avicenne.
  7. ^ "Dyson Cordless Vacuum Comparison Chart: Comparing Best With The Best - Powertoollab". Best Power Tools For Sale, Expert Reviews and Guides. 2018-08-22.
  8. ^ Jump up to: a b Yuka Obayashi, Ritsuko Shimizu (2018-09-13). "Japan's Sumitomo to focus on battery material supply to Panasonic, Toyota". Reuters.
  9. ^ 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". evobsession.com.
  10. ^ Frank Liu (2019-11-13). "Construction of 50,000 mt NCA cathode material project began in Qinghai". SMM news – news.metal.com > news > industry news. Shanghai Metals Market SMM, SMM Information & Technology Co.
  11. ^ Jump up to: a b c d 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, pp. 5–49, doi:10.1007/978-1-4614-5791-6_2, ISBN 978-1-4614-5790-9
  12. ^ Evan Leon (2018-10-26). "From Mine to Market: Energy Metals & Electric Vehicle Industrialization" (PDF). energy.umich.edu. University of Michigan Energy Institute.
  13. ^ Sheng S. Zhang (January 2020), "Problems and their origins of Ni-rich layered oxide cathode materials", Energy Storage Materials, 24, pp. 247–254, doi:10.1016/j.ensm.2019.08.013
  14. ^ Jump up to: a b Xuan Liu, Kang Li, Xiang Li (2018), "The Electrochemical Performance and Applications of Several Popular Lithium-ion Batteries for Electric Vehicles – A Review" (PDF), Advances in Green Energy Systems and Smart Grid, Singapore: Springer Singapore, 925, pp. 201–213, doi:10.1007/978-981-13-2381-2_19, ISBN 978-981-1323-80-5, retrieved 2020-02-15CS1 maint: multiple names: authors list (link)
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