Lithium nickel manganese cobalt oxides

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Lithium nickel manganese cobalt oxides (abbreviated Li-NMC, LNMC, NMC or NCM) are mixed metal oxides of lithium, nickel, manganese and cobalt. They have the general formula LiNixMnyCozO2. The most important representatives have a composition with x + y + z that is near 1, with a small amount of lithium on the transition metal site. In commercial NMC samples, the composition typically has < 5% excess lithium.[1][2] Structurally materials in this group are closely related to lithium cobalt(III) oxide (LiCoO2) and have a layered structure but possess an ideal charge distribution of Mn(IV), Co(III), and Ni(II) at the 1:1:1 stoichiometry. For more nickel-rich compositions, the nickel is in a more oxidized state for charge balance. NMCs are among the most important storage materials for lithium ions in lithium ion batteries. They are used on the positive side, which acts as the cathode during discharge.

History[]

Stoichiometric NMC cathodes are represented as points in the solid solutions between end members, LiCoO2, LiMnO2, and LiNiO2. They are historically derived from John B. Goodenoughs 1980s work on LiCoO2, Tsutomo Ohzuku's work on Li(NiMn)O2, and related studies on NaFeO2-type materials.[3][4] Related to the stoichiometric NMCs, lithium-rich NMC materials were first reported in 1998 and are structurally similar to lithium cobalt(III) oxide (LiCoO2) but stabilized with an excess of lithium, Li/NMC > 1.0, which manifests itself as a series of Li2MnO3-like nanodomains in the materials. These cathodes were first reported by C. S. Johnson, J. T. Vaughey, M. M. Thackeray, T. E. Bofinger, and S. A. Hackney.[5] For both types of NMC cathodes, there is a formal internal charge transfer that oxidizes the manganese and reduces the nickel cations, rather than all the transition metal cations being trivalent. The two electron oxidation of the formally nickel (II) on charging contributes to the high capacity of these NMC cathode materials. In 2001 Arumugam Manthiram postulated that the mechanism that creates the high capacity for layered oxide cathodes such as these results from a transition that can be understood based on the relative positions of the metal 3d band relative to the top of the oxygen 2p band.[6][7][8] This observation helps explain the high capacity of NMC cathodes as above 4.4 V (vs Li) some of the observed capacity has been found to arise from oxidation of the oxide lattice rather than cation oxidation.

In 2001, Christopher Johnson, Michael Thackeray, Khalil Amine, and Jaekook Kim filed a patent[9][10] for lithium nickel manganese cobalt oxide (NMC) lithium rich cathodes based on a Li2MnO3 derived domain structure. In 2001, Zhonghua Lu and Jeff Dahn filed a patent[11] for the NMC class of positive electrode materials, based on the solid solution concept between end-members.

Metal ratios[]

Several different levels of nickel are of commercial interest. The ratio between the three metals is indicated by three numbers. For example, LiNi 0.333Mn0.333Co 0.333O2 is abbreviated to NMC111 or NMC333, LiNi0.5Mn0.3Co0.2O2 to NMC532 (or NCM523), LiNi0.6Mn0.2Co0.2O2 to NMC622 and LiNi0.8Mn0.1Co0.1O2 to NMC811. In view of potential issues with cobalt sourcing, there is interest in increasing the level of nickel, even though this lowers thermal stability.[12]

While either lithium carbonate or lithium hydroxide can be used to NMC111, lithium hydroxide is required make NMC811 as a lower synthesis temperature helps mitigate lithium/nickel site exchange, which has been connected to reduced performance.[13]

Use of NMC electrodes[]

Audi e-tron Sportback

NMC batteries are found in most electric cars. NMC batteries were installed in the BMW ActiveE in 2011/2011, and from 2013 in the BMW i8.[14] Electric cars with NMC batteries include, as of 2020: Audi e-tron GE, BAIC EU5 R550, BMW i3, BYD Yuan EV535, Chevrolet Bolt, Hyundai Kona Electric, Jaguar I-Pace, Jiangling Motors JMC E200L, NIO ES6, Nissan Leaf S Plus, Renault ZOE, Roewe Ei5, VW e-Golf and VW ID.3.[15] There are only a few electric car manufacturers that do not use NMC in their traction batteries. The most important exception is Tesla, as Tesla uses NCA batteries for its vehicles. However, the home storage Tesla Powerwall is said[according to whom?] to be based on NMC.[16]

Jaguar I-Pace

NMC is also used for mobile electronics such as mobile phones/smartphones, laptops in most pedelec[17] batteries.[18] For these applications, batteries with lithium cobalt oxide LCO were still used almost exclusively in 2008.[19] Another application of NMC batteries are battery storage power stations. In Korea, for example, two such storage systems with NMC for frequency regulation were installed in 2016: one with 16 MW capacity and 6 MWh energy and one with 24 MW and 9 MWh.[20] In 2017/2018, a battery with over 30 MW capacity and 11 MWh was installed and commissioned in Newman in the Australian state of Western Australia.[21][22]

Properties of NMC electrodes[]

The cell voltage of lithium ion batteries with NMC is 3.6–3.7 V.[23] Manthiram discovered that the capacity limitations of these layered oxide cathodes is a result of chemical instability that can be understood based on the relative positions of the metal 3d band relative to the top of the oxygen 2p band.[24][25][26] This discovery has had significant implications for the practically accessible compositional space of lithium ion batteries, as well as their stability from a safety perspective.

References[]

  1. ^ Julien, Christian; Monger, Alain; Zaghib, Karim; Groult, Henri (July 2016). "Optimization of Layered Cathode Materials for Lithium-Ion Batteries". Materials (Basel). 9 (7): 595. Bibcode:2016Mate....9..595J. doi:10.3390/ma9070595. PMC 5456936. PMID 28773717.
  2. ^ Li, Xuemen; Colclasure, Andrew; Finegan, Donal; Ren, Dongsheng; Shi, Ying; Feng, Xuning; Cao, Lei; Yang, Yuan; Smith, Kandler (February 2019). "Degradation Mechanisms of High Capacity 18650 Cells Containing Si-Graphite Anode and Nickel-Rich NMC Cathode". Electrochimica Acta. 297: 1109–1120. doi:10.1016/j.electacta.2018.11.194. OSTI 1491439. S2CID 104299816.
  3. ^ Mizushima, K.; Jones, P.C.; Wiseman, P.J.; Goodenough, J.B. (1980). "LixCoO2 (0<x<-1): A new cathode material for batteries of high energy density". Materials Research Bulletin. 15 (6): 783–789. doi:10.1016/0025-5408(80)90012-4.
  4. ^ Breger, Julian; Dupre, Nicolas; Chupas, Peter; Lee, Peter; Proffen, Thomas; Parise, John; Grey, Clare (2005). "Short- and Long-Range Order in the Positive Electrode Material, Li(NiMn)0.5O2: A Joint X-ray and Neutron Diffraction, Pair Distribution Function Analysis and NMR Study". Journal of the American Chemical Society. 127 (20): 7529–7537. doi:10.1021/ja050697u. PMID 15898804.
  5. ^ C. S. Johnson, J. T. Vaughey, M. M. Thackeray, T. E. Bofinger, and S. A. Hackney "Layered Lithium-Manganese Oxide Electrodes Derived from Rock-Salt LixMnyOz (x+y=z) Precursors" 194th Meeting of the Electrochemical Society, Boston, MA, Nov.1-6, (1998)
  6. ^ Chebiam, R. V.; Kannan, A. M.; Prado, F.; Manthiram, A. (2001). "Comparison of the chemical stability of the high energy density cathodes of lithium-ion batteries". Electrochemistry Communications. 3 (11): 624–627. doi:10.1016/S1388-2481(01)00232-6.
  7. ^ Chebiam, R. V.; Prado, F.; Manthiram, A. (2001). "Soft Chemistry Synthesis and Characterization of Layered Li1−xNi1−yCoyO2−δ (0 ≤ x ≤ 1 and 0 ≤ y ≤ 1)". Chemistry of Materials. 13 (9): 2951–2957. doi:10.1021/cm0102537.
  8. ^ Manthiram, Arumugam (2020). "A reflection on lithium-ion battery cathode chemistry". Nature Communications. 11 (1): 1550. Bibcode:2020NatCo..11.1550M. doi:10.1038/s41467-020-15355-0. PMC 7096394. PMID 32214093.
  9. ^ US US6677082, Thackeray, M; Amine, K. & Kim, J. S., "Lithium metal oxide electrodes for lithium cells and batteries" 
  10. ^ US US6680143, Thackeray, M; Amine, K. & Kim, J. S., "Lithium metal oxide electrodes for lithium cells and batteries" 
  11. ^ US US6964828 B2, Lu, Zhonghua, "Cathode compositions for lithium-ion batteries" 
  12. ^ Sun, Xin; Luo, Xiaoli; Zhang, Zhan; Meng, Fanran; Yang, Jianxin (November 2020). "Life cycle assessment of lithium nickel cobalt manganese oxide (NCM) batteries for electric passenger vehicles". Journal of Cleaner Production. 273: 123006. doi:10.1016/j.jclepro.2020.123006. S2CID 225028954.
  13. ^ Zhao, Enyue; Fang, Lincan; Chen, Minmin; Chen, Dongfeng; Wang, Qingzhen; Hu, Zhongbo; Yan, Qing-Bo; Wu, Meimei; Xiao, Xiaoling (2017). "New insight into Li/Ni disorder in layered cathode materials for lithium ion batteries: a joint study of neutron diffraction, electrochemical kinetic analysis and first-principles calculations". Journal of Materials Chemistry A. 5 (4): 1679–1686. doi:10.1039/C6TA08448F.
  14. ^ Apurba Sakti; Jeremy J. Michalek; Erica R.H. Fuchs; Jay F. Whitacre (2015-01-01), "A techno-economic analysis and optimization of Li-ion batteries for light-duty passenger vehicle electrification" (PDF), Journal of Power Sources, vol. 273, pp. 966–980, Bibcode:2015JPS...273..966S, doi:10.1016/j.jpowsour.2014.09.078, retrieved 2020-02-23
  15. ^ Wangda Li; Evan M. Erickson; Arumugam Manthiram (January 2020), "High-nickel layered oxide cathodes for lithium-based automotive batteries", Nature Energy, Springer Nature, vol. 5, no. 1, pp. 26–34, Bibcode:2020NatEn...5...26L, doi:10.1038/s41560-019-0513-0, ISSN 2058-7546, S2CID 213811886
  16. ^ Zachary Shahan (2015-05-07). "38,000 Tesla Powerwall Reservations In Under A Week (Tesla / Elon Musk Transcript)". CleanTechnica.
  17. ^ "Batterie - Beschreibung von Batterietypen. Lithium-Ionen-Batterien". Go Pedelec! (in German). energieautark consulting gmbh. 2010-10-27. Die meistverbreitteste Li-ionzelle auf dem Markt ist die Lithium-Nickel-Mangan-Kobalt-Oxid-Zelle (Li-NMC) mit einer Nominalspannung von 3.6 V je Zelle.
  18. ^ Jürgen Garche, Klaus Brandt (2018), Electrochemical Power Sources: Fundamentals, Systems, and Applications: Li-battery safety (1 ed.), Amsterdam, Netherlands: Elsevier, p. 128, ISBN 978-0-444-64008-6, retrieved 2020-02-23
  19. ^ Sébastien Patoux; Lucas Sannier; Hélène Lignier; Yvan Reynier; Carole Bourbon; Séverine Jouanneau; Frédéric Le Cras; Sébastien Martinet (May 2008), "High voltage nickel manganese spinel oxides for Li-ion batteries", Electrochimica Acta, vol. 53, no. 12, pp. 4137–4145, doi:10.1016/j.electacta.2007.12.054
  20. ^ Kokam (2016-03-07). "Kokam's 56 Megawatt Energy Storage Project Features World's Largest Lithium NMC Energy Storage System for Frequency Regulation". PR Newswire. PR Newswire Association LLC.
  21. ^ Giles Parkinson (2019-08-12). "Alinta sees sub 5-year payback for unsubsidised big battery at Newman". RenewEconomy.
  22. ^ "Energy Storage Solution Provider" (PDF).
  23. ^ Peter Miller (2015), "Automotive Lithium-Ion Batteries", Johnson Matthey Technology Review, vol. 59, no. 1, pp. 4–13, doi:10.1595/205651315X685445
  24. ^ Chebiam, R. V.; Kannan, A. M.; Prado, F.; Manthiram, A. (2001). "Comparison of the chemical stability of the high energy density cathodes of lithium-ion batteries". Electrochemistry Communications. 3 (11): 624–627. doi:10.1016/S1388-2481(01)00232-6.
  25. ^ Chebiam, R. V.; Prado, F.; Manthiram, A. (2001). "Soft Chemistry Synthesis and Characterization of Layered Li1−xNi1−yCoyO2−δ (0 ≤ x ≤ 1 and 0 ≤ y ≤ 1)". Chemistry of Materials. 13: 2951–2957. doi:10.1021/cm0102537.
  26. ^ Manthiram, Arumugam (2020). "A reflection on lithium-ion battery cathode chemistry". Nature Communications. 11 (1): 1550. Bibcode:2020NatCo..11.1550M. doi:10.1038/s41467-020-15355-0. PMC 7096394. PMID 32214093.
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