Lithium-Nickel-Cobalt-Aluminum Oxides

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The lithium-nickel-cobalt-aluminum oxides , or NCA for short , form a group of oxides . Their most important representatives are important because of their application in lithium ion accumulators . There they are used as active material on the positive side, which is the cathode when the battery is discharged . They are mixed oxides with the cations of lithium , nickel , cobalt and aluminum . The most important representatives have the general formula LiNi x Co y Al z O 2 with x  +  y  +  z  = 1. For the currently commercially available batteries with NCA, which are also used in electric cars and electrical appliances , x  ≈ 0.8, and the voltage of the batteries is between 3.6 V and 4.0 V, with a nominal voltage of 3.6 V or 3.7 V. A variant of the oxides that is current in 2019 is LiNi 0.84 Co 0.12 Al 0.04 O 2 .

NCA accumulators: manufacturer and use

Tesla's vehicles - here a Model 3 - are powered by NCA batteries.
The motors of the Model X series also run on electricity from NCA batteries.

The most important manufacturer of NCA batteries is Panasonic or Panasonic's cooperation partner Tesla , since Tesla uses NCA as an active material in the traction batteries of its automobile models. LiNi 0.84 Co 0.12 Al 0.04 O 2 is used in the Tesla Model 3 and Tesla Model X models. With a few exceptions, current electric cars are using either NCA or alternatively lithium-nickel-manganese-cobalt-oxide NMC as of 2019 . In addition to being used in electric cars, NCA is also used in batteries for electronic devices, mainly from Panasonic, Sony and Samsung . Cordless vacuum cleaners are also equipped with NCA batteries.

Manufacturer of NCA

The most important NCA producers 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%. Sumitomo supplies Tesla and Panasonic and was able to produce 850 tons of NCA per month in 2014. In 2016 Sumitomo increased its monthly production capacity to 2550 tons, in 2018 to 4550 tons. In China, in Tongren County in the Qinghai Province , a plant has been under construction since 2019, which will initially produce 1,500 tons of NCA per month.

Properties of NCA in comparison

The usable capacity of the charge storage of NCA is around 0.18 to 0.20 Ah / g. This is well below the theoretical values; for LiNi 0.8 Co 0.15 Al 0.05 O 2 this is 279 mAh / g. The capacity of NCA is, however, significantly higher than alternative materials, e.g. B. Lithium cobalt oxide LiCoO 2 with 148 mAh / g, lithium iron phosphate LiFePO 4 with 165 mAh / g and NMC 333 LiNi 0.33 Mn 0.33 Co 0.33 O 2 with 170 mAh / g. Like LiCoO 2 and NMC, NCA is one of the cathode materials with a layer structure. Due to the high voltage, NCA enables batteries with high energy density. Another benefit of NCA is its excellent quick-charge capability. Disadvantages are the high costs and the limited resources of cobalt and nickel.

The two substance types NCA and NMC have related structures, a very similar electrochemical behavior and similar performance data, which enable relatively high energy densities and relatively high performances for both. The Model 3 NCA battery is estimated to hold between 4.5 and 9.5 kg of cobalt and 11.6 kg of Li.

Crystal structure of nickel (IV) oxide

The lithium nickel oxide LiNiO 2, which is closely related to NCA, or the nickel oxide NiO 2 itself cannot be used as a battery material so far, since it is mechanically unstable, shows a rapid loss of capacity and has safety problems.

Nickel Rich NCA, Pros and Problems

Representatives of the NCA material group LiNi x Co y Al z O 2 with x  ≥ 0.8 are called nickel-rich ( English Ni-rich ); they are the most important representatives of the entire NCA class of substances. The nickel-rich variants are at the same time low in cobalt and therefore have a cost advantage, since cobalt is relatively expensive. In addition, the higher the nickel content, the higher the voltage, and thus the energy that can be stored in the battery. However, the higher the nickel content, the greater the risk of thermal runaway and premature aging of the battery. If a typical NCA battery is heated to 180 ° C, it will thermally break down. If the battery was previously overcharged while charging, thermal runaway can start at 65 ° C. The aluminum ions in the NCA increase stability and safety, but they decrease capacity because they do not take part in oxidation and reduction themselves.

Modifications of the material

In order to make NCA more resistant, especially if the battery is to function at temperatures above 50 ° C., the NCA active material is usually coated. The coatings used in research consisted of fluorides such as aluminum fluoride AlF 3 , of crystalline (e.g. CoO 2 , TiO 2 , NMC) or vitreous ( SiO 2 ) oxides or of phosphates such as FePO 4 .

Individual evidence

  1. ↑ a b c d Agus Purwanto, Cornelius Satria Yudha, U Ubaidillah, Hendri Widiyandari, Takashi Ogi: NCA cathode material: synthesis methods and performance enhancement efforts . In: Materials Research Express . tape 5 , no. 12 . IOP Publishing, September 26, 2018, ISSN  2053-1591 , p. 122001 , doi : 10.1088 / 2053-1591 / aae167 .
  2. ↑ James Ayre: Tesla Batteries 101 - Production Capacity, Uses, Chemistry, & Future Plans. In: CleanTechnica cleantech-focused news & analysis. CleanTechnica, December 2, 2017, accessed December 2, 2020 (American English).
  3. ↑ Fred Lambert: Tesla battery researcher unveils new chemistry to increase lifecycle at high voltage. In: Electrek. Electrek, 9to5 network, May 4, 2017, accessed February 12, 2020 (American English).
  4. ↑ a b c Matteo Bianchini, Maria Roca-Ayats, Pascal Hartmann, Torsten Brezesinski, Jürgen Janek: There and Back Again-The Journey of LiNiO 2 as a Cathode Active Material . In: Angewandte Chemie International Edition . tape 58 , no. 31 . Wiley-VCH, July 29, 2019, p. 10434-10458 , doi : 10.1002 / anie.201812472 .
  5. ↑ Gyeong Won Nam, Nam-Yung Park, Kang-Joon Park, Jihui Yang, Jun Liu: Capacity Fading of Ni-Rich NCA Cathodes: Effect of Microcracking Extent . In: ACS Energy Letters . tape 4 , no. 12 , December 13, 2019, ISSN  2380-8195 , p. 2995-3001 , doi : 10.1021 / acsenergylett.9b02302 .
  6. ↑ a b Christophe Pillot: Lithium ion battery raw material Supply & demand 2016–2025. (PDF) In: avicenne.com. Avicenne, January 30, 2017, accessed February 16, 2020 .
  7. ↑ Dyson Cordless Vacuum Comparison Chart: Comparing Best With The Best - Powertoollab. In: Best Power Tools For Sale, Expert Reviews and Guides. August 22, 2018. Retrieved February 22, 2020 (American English).
  8. ↑ a b Yuka Obayashi, Ritsuko Shimizu: Japan's Sumitomo to focus on battery material supply to Panasonic, Toyota. In: Reuters. September 13, 2018, accessed February 17, 2020 .
  9. ↑ James Ayre: Sumitomo Metal Mining Boosting NCA (Used In Lithium-Ion Cathodes) Production By 38%, In Anticipation Of Tesla Model 3 Launch. In: evobsession.com. February 26, 2016, accessed February 16, 2020 .
  10. ^ Frank Liu: Construction of 50,000 mt NCA cathode material project began in Qinghai. In: SMM news - news.metal.com> news> industry news. Shanghai Metals Market SMM, SMM Information & Technology Co, November 13, 2019, accessed on February 22, 2020 .
  11. ↑ a b c d Marca M. Doeff: Battery Cathodes . Selected Entries from the Encyclopedia of Sustainability Science and Technology. In: Ralph J. Brodd (Ed.): Batteries for Sustainability . Springer, New York, NY 2013, ISBN 978-1-4614-5790-9 , pp. 5-49 , doi : 10.1007 / 978-1-4614-5791-6_2 .
  12. ^ Evan Leon: From Mine to Market: Energy Metals & Electric Vehicle Industrialization. (PDF) In: energy.umich.edu. University of Michigan Energy Institute, October 26, 2018, accessed February 15, 2020 .
  13. ↑ Sheng S. Zhang: Problems and their origins of Ni-rich layered oxide cathode materials . In: Energy Storage Materials . tape January 24 , 2020, p. 247–254 , doi : 10.1016 / j.ensm.2019.08.013 .
  14. ^ A b Xuan Liu, Kang Li, Xiang Li: The Electrochemical Performance and Applications of Several Popular Lithium-ion Batteries for Electric Vehicles - A Review . In: Advances in Green Energy Systems and Smart Grid . tape 925 . Springer Singapore, Singapore 2018, ISBN 978-981-13-2380-5 , pp. 201–213 , doi : 10.1007 / 978-981-13-2381-2_19 ( preliminary version online [PDF; accessed on February 15, 2020]).