Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Perspective
  • Published:

High-nickel layered oxide cathodes for lithium-based automotive batteries

Abstract

High-nickel layered oxide cathode materials will be at the forefront to enable longer driving-range electric vehicles at more affordable costs with lithium-based batteries. A continued push to higher energy content and less usage of costly raw materials, such as cobalt, while preserving acceptable power, lifetime and safety metrics, calls for a suite of strategic compositional, morphological and microstructural designs and efficient material production processes. In this Perspective, we discuss several important design considerations for high-nickel layered oxide cathodes that will be implemented in the automotive market for the coming decade. We outline various intrinsic restraints of maximizing their energy output and compare current/emerging development roadmaps approaching low-/zero-cobalt chemistry. Materials production is another focus, relevant to driving down costs and addressing the practical challenges of high-nickel layered oxides for demanding vehicle applications. We further assess a series of stabilization techniques on their prospects to fulfill the aggressive targets of vehicle electrification.

This is a preview of subscription content, access via your institution

Access options

Buy this article

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Lithium-ion batteries for the automotive market and cathode material landscape.
Fig. 2: Compositional design principles of high-energy, low-cobalt layered oxides.
Fig. 3: Production and conditioning processes for high-energy, low-cobalt layered oxides.

Similar content being viewed by others

References

  1. Irle, R. Global EV sales for 2018 – final results. EV-volumes.com http://www.ev-volumes.com/news/global-ev-sales-for-2018/ (2019).

  2. Global EV Outlook 2019 (International Energy Agency, 2019).

  3. The Push to High Nickel Content in Layered Oxides – Production, Cost, and Supply & Demand (in Chinese) (Shanxi Securities, 2019).

  4. Alvarez, S. Tesla model 3 battery details revealed in partial teardown and analysis. Teslarati https://www.teslarati.com/tesla-model-3-battery-details-partial-teardown-analysis (2018).

  5. Goldie-Scot, L. A behind the scenes take on lithium-ion battery prices Bloomberg New Energy Finance https://about.bnef.com/blog/behind-scenes-take-lithium-ion-battery-prices/ (2019).

  6. US DRIVE Electrochemical Energy Storage Technical Team Roadmap (US Council for Automotive Research, 2017).

  7. Schmuch, R., Wagner, R., Hörpel, G., Placke, T. & Winter, M. Performance and cost of materials for lithium-based rechargeable automotive batteries. Nat. Energy 3, 267–278 (2018).

    Article  Google Scholar 

  8. Kwade, A. et al. Current status and challenges for automotive battery production technologies. Nat. Energy 3, 290–300 (2018).

    Article  Google Scholar 

  9. Fang, Q. NCM/NCA vs. LFP: the Competitive Edge of LFP (in Chinese). China Battery Enterprise Alliance (March 2019).

  10. China’s installed battery capacity surges to 56.9 GWh. InsideEVs https://insideevs.com/news/342285/chinas-installed-battery-capacity-surges-to-569-gwh/ (2019).

  11. Pillot, C. Lithium Ion Battery Raw Materials Supply and Demand 2016–2025 (AABC Europe, 2017); http://cii-resource.com/cet/AABE-03-17/Presentations/BRMT/Pillot_Christophe.pdf

  12. Myung, S.-T. et al. Nickel-rich layered cathode materials for automotive lithium-ion batteries: achievements and perspectives. ACS Energy Lett. 2, 196–223 (2017).

    Article  Google Scholar 

  13. Kim, J. et al. Prospect and reality of Ni-rich cathode for commercialization. Adv. Energy Mater. 8, 1702028 (2018).

    Article  Google Scholar 

  14. Mineral Commodity Summaries 2018 (US Geological Survey, 2018).

  15. Li, W., Yaghoobnejad Asl, H., Xie, Q. & Manthiram, A. Collapse of LiNi1-x-yCoxMnyO2 lattice at deep charge irrespective of Ni content in lithium-ion batteries. J. Am. Chem. Soc. 141, 5097–5101 (2019).

    Article  Google Scholar 

  16. Wandt, J., Freiberg, A. T. S., Ogrodnik, A. & Gasteiger, H. A. Singlet oxygen evolution from layered transition metal oxide cathode materials and its implications for lithium-ion batteries. Mater. Today 21, 825–833 (2018).

    Article  Google Scholar 

  17. Gilbert, J. A., Shkrob, I. A. & Abraham, D. P. Transition metal dissolution, ion migration, electrocatalytic reduction and capacity loss in lithium-ion full cells. J. Electrochem. Soc. 164, A389–A399 (2017).

    Article  Google Scholar 

  18. Lin, F. et al. Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries. Nat. Commun. 5, 3529 (2014).

    Article  Google Scholar 

  19. Ma, L., Nie, M., Xia, J. & Dahn, J. R. A systematic study on the reactivity of different grades of charged Li[NixMnyCoz]O2 with electrolyte at elevated temperatures using accelerating rate calorimetry. J. Power Sources 327, 145–150 (2016).

    Article  Google Scholar 

  20. Ohzuku, T., Ueda, A. & Nagayama, M. Electrochemistry and structural chemistry of LiNiO2 \((R\overline{3}{\rm{m}})\) for 4 volt secondary lithium cells. J. Electrochem. Soc. 140, 1862–1870 (1993).

    Article  Google Scholar 

  21. You, Y., Celio, H., Li, J., Dolocan, A. & Manthiram, A. Modified high‐nickel cathodes with stable surface chemistry against ambient air for lithium‐ion batteries. Angew. Chem. Int. Ed. 57, 6480–6485 (2018).

    Article  Google Scholar 

  22. Renfrew, S. E. & McCloskey, B. D. Residual lithium carbonate predominantly accounts for first cycle CO2 and CO outgassing of Li-stoichiometric and Li-rich layered transition-metal oxides. J. Am. Chem. Soc. 139, 17853–17860 (2017).

    Article  Google Scholar 

  23. Yakovleva, M. From Raw Material to Next Generation Advanced Batteries (FMC Corporation, 2017).

  24. Production and Cost Analysis of Nickel-Rich Layered Cathode Materials (in Chinese) (CITIC Securities, 2018).

  25. Panasonic starts mass-production of high-capacity 3.1 Ah lithium-ion battery. Panasonic Newsroom Global https://news.panasonic.com/global/press/data/en091218-2/en091218-2.html (2009).

  26. Jeong, M. H., Lee, J. H. & Jung, S. H. Electrolyte for lithium secondary battery and lithium secondary battery comprising same. US Patent 20,180,183,100 A1 (2018).

  27. Vandeputte, K. Price elasticity of supply for cathode materials in a fast-growing vehicle electrification scenario. In Proc. Commercializing Advanced High-Energy Batteries for Heavy & Light EVs (AABC Europe, 2019).

  28. Fiscal Year 2018 Advanced Vehicle Technologies Research Funding Opportunity Announcement (FOA): 1a. Developing Low-Cobalt Active Cathode Materials for Next-Generation Li-Ion Batteries. DOE DE-FOA-0001919 (US Department of Energy, 2018).

  29. Delmas, C., Saadoune, I. & Rougier, A. The Cycling Properties of the LixNi1−yCoyO2 Electrode. J. Power Sources 44, 595–602 (1993).

    Article  Google Scholar 

  30. Ohzuku, T., Ueda, A. & Kouguchi, M. Synthesis and characterization of LiAl1/4Ni3/4O2 \(({\rm{R}}\overline{3}{\rm{m}})\) for lithium‐ion (shuttlecock) batteries. J. Electrochem. Soc. 142, 4033–4039 (1995).

    Article  Google Scholar 

  31. Guilmard, M., Rougier, A., Grüne, M., Croguennec, L. & Delmas, C. Effects of aluminum on the structural and electrochemical properties of LiNiO2. J. Power Sources 115, 305–314 (2003).

    Article  Google Scholar 

  32. Arai, H., Okada, S., Sakurai, Y. & Yamaki, J. Electrochemical and thermal behavior of LiNi1−zMzO2 (M = Co, Mn, Ti). J. Electrochem. Soc. 144, 3117–3125 (1997).

    Article  Google Scholar 

  33. Li, H. et al. Is cobalt needed in Ni-rich positive electrode materials for lithium ion batteries? J. Electrochem. Soc. 166, A429–A439 (2019).

    Article  Google Scholar 

  34. Watanabe, S., Kinoshita, M., Hosokawa, T., Morigaki, K. & Nakura, K. Capacity fading of LiAlyNi1−xyCoxO2 cathode for lithium-ion batteries during accelerated calendar and cycle life tests (effect of depth of discharge in charge-discharge cycling on the suppression of the micro-crack generation of LiAlyNi1−xyCoxO2 Particle). J. Power Sources 260, 50–56 (2014).

    Article  Google Scholar 

  35. Li, W. et al. Mn versus Al in layered oxide cathodes in lithium‐ion batteries: a comprehensive evaluation on long‐term cyclability. Adv. Energy Mater. 8, 1703154 (2018).

    Article  Google Scholar 

  36. Madhavi, S., Subba Rao, G. V., Chowdari, B. V. R. & Li, S. F. Y. Effect of aluminium doping on cathodic behaviour of LiNi0.7Co0.3O2. J. Power Sources 93, 156–162 (2001).

    Article  Google Scholar 

  37. Rossen, E., Jones, C. D. W. & Dahn, J. R. Structure and electrochemistry of LixMnyNi1−yO2. Solid State Ion. 57, 311–318 (1992).

    Article  Google Scholar 

  38. Seiwert, M. VW’s Batteries Contain Four Times as much Cobalt as Tesla Batteries (in German) (WirtschaftsWoche, 2019).

  39. Fortuna, C. Cobalt-Free Car Batteries In the Works for Panasonic & Tesla. Clean Technica https://cleantechnica.com/2018/06/09/cobalt-free-car-batteries-in-the-works-for-panasonic-tesla/ (2018).

  40. Lima, P. NIO Begins Deliveries of ES6 with NCM 811 Battery. PushEVs https://pushevs.com/2019/06/20/nio-begins-deliveries-of-es6-with-ncm-811-battery/ (2019).

  41. Son, Y. S. & Hong, J. Method of fabricating cathode active material of lithium secondary battery. US Patent 20,180,034,050 A1 (2018).

  42. Johnson Matthey achieves two major milestones in journey to commercialise eLNO. JM News https://matthey.com/news/2019/johnson-matthey-achieves-two-major-milestones-in-commercialisation-of-elno (2019).

  43. Bianchini, M., Roca-Ayats, M., Hartmann, P., Brezesinski, T. & Janek, J. There and back again –the journey of LiNiO2 as a cathode active material. Angew. Chem. Int. Ed. 58, 2–27 (2019).

    Article  Google Scholar 

  44. Weigel, T. et al. Structural and electrochemical aspects of LiNi0.8Co0.1Mn0.1O2 cathode materials doped by various cations. ACS Energy Lett. 4, 508–516 (2019).

    Article  Google Scholar 

  45. Kim, U.-H. et al. Pushing the limit of layered transition metal oxide cathodes for high-energy density rechargeable Li ion batteries. Energy Environ. Sci. 11, 1271–1279 (2018).

    Article  Google Scholar 

  46. Turcheniuk, K., Bondarev, D., Singhal, V. & Yushin, G. Ten years left to redesign lithium-ion batteries. Nature 31, 467–470 (2018).

    Article  Google Scholar 

  47. Sun, Y.-K., Myung, S.-T., Kim, M.-H., Prakash, J. & Amine, K. Synthesis and characterization of Li[(Ni0.8Co0.1Mn0.1)0.8(Ni0.5Mn0.5)0.2]O2 with the microscale core-shell structure as the positive electrode material for lithium batteries. J. Am. Chem. Soc. 127, 13411–13418 (2005).

    Article  Google Scholar 

  48. Fiscal Year 1983 - 2019 SBIR/STTR Awards (US Small Business Administration, 2019).

  49. Li, W., Kim, U.-H., Dolocan, A., Sun, Y.-K. & Manthiram, A. Formation and inhibition of metallic lithium microstructures in lithium batteries driven by chemical crossover. ACS Nano 11, 5853–5863 (2017).

    Article  Google Scholar 

  50. Toya, H. N. et al. Nickel-cobalt-manganese complex hydroxide particles and method for producing same, positive electrode active material for nonaqueous electrolyte secondary battery and method for producing same, and nonaqueous electrolyte secondary battery. US Patent 20,120,270,107 A1 (2012).

  51. Liu, Y., Zhu, Y. & Cui, Y. Challenges and opportunities towards fast-charging battery materials. Nat. Energy 4, 540–550 (2019).

    Article  Google Scholar 

  52. Muto, S. et al. Capacity-fading mechanisms of LiNiO2-based lithium-ion batteries: ii. diagnostic analysis by electron microscopy and spectroscopy. J. Electrochem. Soc. 156, A371–A377 (2009).

    Article  Google Scholar 

  53. Orikasa, Y. et al. Ionic conduction in lithium ion battery composite electrode governs cross-sectional reaction distribution. Sci. Rep. 6, 26382 (2016).

    Article  Google Scholar 

  54. Pullen, A., Rempel, J. & Sriramulu, S. Polycrystalline layered metal oxides comprising nano-crystals. US Patent 20,190,140,276 A1 (2019).

  55. Kim, J. et al. Nickel-based active material for lithium secondary battery, method of preparing the same, and lithium secondary battery including positive electrode including the nickel-based active material. US Patent 20,180,026,268 A1 (2018).

  56. Yan, P. et al. Tailoring grain boundary structures and chemistry of Ni-rich layered cathodes for enhanced cycle stability of lithium-ion batteries. Nat. Energy 3, 600–605 (2018).

    Article  Google Scholar 

  57. Li, J. et al. Comparison of single crystal and polycrystalline LiNi0.5Mn0.3Co0.2O2 positive electrode materials for high voltage Li-ion cells. J. Electrochem. Soc. 164, A1534–A1544 (2017).

    Article  Google Scholar 

  58. Park, S., Chang, S. K., Park, H.-K., Hong, S. T. & Choi, Y. Electrode active material for lithium secondary battery. US Patent 20,140,356,719 A1 (2014).

  59. Kimijima, T., Zettsu, N. & Teshima, K. Growth manner of octahedral-shaped Li(Ni1/3Co1/3Mn1/3)O2 single crystals in molten Na2SO4. Cryst. Growth Des. 16, 2618–2623 (2016).

    Article  Google Scholar 

  60. Han, X., Meng, Q., Sun, T. & Sun, J. Preparation and electrochemical characterization of single-crystalline spherical LiNi1/3Co1/3Mn1/3O2 powders cathode material for Li-Ion Batteries. J. Power Sources 195, 3047–3052 (2010).

    Article  Google Scholar 

  61. Kim, J. et al. A highly stabilized nickel-rich cathode material by nanoscale epitaxy control for high-energy lithium-ion batteries. Energy Environ. Sci. 11, 1449–1459 (2018).

    Article  Google Scholar 

  62. Myung, S.-T. et al. Role of alumina coating on Li-Ni-Co-Mn-O particles as positive electrode material for lithium-ion batteries. Chem. Mater. 17, 3695–3704 (2005).

    Article  Google Scholar 

  63. Son, I. H., Park, J. H., Kwon, S., Mun, J. & Choi, J. W. Self-terminated artificial SEI Layer for nickel-rich layered cathode material via mixed gas chemical vapor deposition. Chem. Mater. 27, 7370–7379 (2015).

    Article  Google Scholar 

  64. Maydannik, P. S., Kaariainen, T. O. & Cameron, D. C. Continuous atomic layer deposition: explanation for anomalous growth rate effects. J. Vac. Sci. Technol. A 30, 01A122 (2011).

    Article  Google Scholar 

  65. Duong, H. M., Feigenbaum, H. & Hong, J. Dry energy storage device electrode and methods of making the same. US Patent, 20,150,303,481 A1 (2015).

  66. Chiang, Y.-M., Duduta, M., Holman, R., Limthongkul, P. & Tan, T. Semi-solid electrodes having high rate capability. US Patent 20,140,170,524 A1 (2014).

Download references

Acknowledgements

The authors gratefully acknowledge the support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy through the award number DE-EE0008445 and the Welch Foundation F-1254.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Arumugam Manthiram.

Ethics declarations

Competing interests

The authors have founded a startup company called TexPower to develop low-cobalt and cobalt-free cathode materials for lithium-based batteries.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Li, W., Erickson, E.M. & Manthiram, A. High-nickel layered oxide cathodes for lithium-based automotive batteries. Nat Energy 5, 26–34 (2020). https://doi.org/10.1038/s41560-019-0513-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41560-019-0513-0

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing