Current bottlenecks in cobalt (Co) supply have negatively impacted commercial battery production and inspired the development of cathode materials that are less reliant on Co. However, complete Co elimination is prevented by the lack of fundamental understanding of the impact of Co on cathode capacity and structural stability, as well as the lack of effective substitute components in practice. Here we investigate the roles of Co in purposely designed systems that include both Co-rich and Mn-substituted Co-free cathodes. Our results affirmed that Co plays an undeniable role in fast capacity and/or structural degradation, and found that Co is more destructive than Ni at high potentials, which offers unexpected but encouraging perspectives for Co reduction. Moreover, Mn substitution effectively alleviates the destructive effects of Co and enables a high potential functionality. With these fundamental discoveries, we demonstrated a series of LiNiαMnβXγO2 (X = single or multiple dopants) as a promising candidate for Co-free cathodes.
Subscribe to Journal
Get full journal access for 1 year
only $4.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
All the relevant data are included in the paper and its Supplementary Information.
Wang, X., Ding, Y. L., Deng, Y. P. & Chen, Z. Ni-rich/Co-poor layered cathode for automotive Li-ion batteries: promises and challenges. Adv. Energy Mater. 10, 1903864 (2020).
Li, H. et al. Is cobalt needed in Ni-rich positive electrode materials for lithium ion batteries? J. Electrochem. Soc. 166, A429–A439 (2019).
Olivetti, E. A., Ceder, G., Gaustad, G. G. & Fu, X. Lithium-ion battery supply chain considerations: analysis of potential bottlenecks in critical metals. Joule 1, 229–243 (2017).
Bessette, S. et al. Nanoscale lithium quantification in LixNiyCowMnzO2 as cathode for rechargeable batteries. Sci. Rep. 8, 1–9 (2018).
Zhang, J.-N. et al. Trace doping of multiple elements enables stable battery cycling of LiCoO2 at 4.6 V. Nat. Energy 4, 594–603 (2019).
Tsai, P. C. et al. Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries. Energy Environ. Sci. 11, 860–871 (2018).
Li, M. & Lu, J. Cobalt in lithium-ion batteries. Science 367, 979–980 (2020).
Hu, E. et al. Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release. Nat. Energy 3, 690–698 (2018).
Liu, T. et al. Correlation between manganese dissolution and dynamic phase stability in spinel-based lithium-ion battery. Nat. Commun. 10, 4721 (2019).
Li, W. et al. Enabling high areal capacity for Co-free high voltage spinel materials in next-generation Li-ion batteries. J. Power Sources 473, 228579 (2020).
Lee, J. et al. Unlocking the potential of cation-disordered oxides for rechargeable lithium batteries. Science 343, 519–522 (2014).
Liu, C., Neale, Z. G. & Cao, G. Understanding electrochemical potentials of cathode materials in rechargeable batteries. Mater. Today 19, 109–123 (2016).
Schipper, F. et al. Review—recent advances and remaining challenges for lithium ion battery cathodes. J. Electrochem. Soc. 164, A6220–A6228 (2016).
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).
Mu, L. et al. The sensitive surface chemistry of Co-free, Ni-rich layered oxides: identifying experimental conditions that influence characterization results. J. Mater. Chem. A 8, 17487–17497 (2020).
Kaboli, S. et al. Behavior of solid electrolyte in Li-polymer battery with NMC cathode via in-situ scanning electron microscopy. Nano Lett. 20, 1607–1613 (2020).
Xiao, Y. et al. Insight into the origin of lithium/nickel ions exchange in layered Li(NixMnyCoz)O2 cathode materials. Nano Energy 49, 77–85 (2018).
Zou, Y. et al. Multishelled Ni-rich Li(NixCoyMnz)O2 hollow fibers with low cation mixing as high-performance cathode materials for Li-ion batteries. Adv. Sci. 4, 1600262 (2017).
Zheng, J. et al. Ni/Li disordering in layered transition metal oxide: electrochemical impact, origin, and control. Acc. Chem. Res. 52, 2201–2209 (2019).
Zheng, Z. et al. Thermodynamically revealing the essence of order and disorder structures in layered cathode materials. Chin. J. Struct. Chem. 38, 2020–2026 (2019).
Zhao, J. Q. et al. In situ probing and synthetic control of cationic ordering in Ni-rich layered oxide cathodes. Adv. Energy Mater. 7, 1601266 (2017).
Zhao, E. Y. et al. 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. J. Mater. Chem. A 5, 1679–1686 (2017).
Duan, Y. D. et al. Insights into Li/Ni ordering and surface reconstruction during synthesis of Ni-rich layered oxides. J. Mater. Chem. A 7, 513–519 (2019).
Zhang, M. J. et al. Cationic ordering coupled to reconstruction of basic building units during synthesis of high-Ni layered oxides. J. Am. Chem. Soc. 140, 12484–12492 (2018).
Kang, K. S., Meng, Y. S., Breger, J., Grey, C. P. & Ceder, G. Electrodes with high power and high capacity for rechargeable lithium batteries. Science 311, 977–980 (2006).
Li, H., Zhang, N., Li, J. & Dahn, J. R. Updating the structure and electrochemistry of LixNiO2 for 0 ≤ x ≤1. J. Electrochem. Soc. 165, A2985–A2993 (2018).
Ryu, H.-H., Park, K.-J., Yoon, C. S. & Sun, Y.-K. Capacity fading of Ni-rich Li[NixCoyMn1–x–y]O2 (0.6 ≤ x ≤ 0.95) cathodes for high-energy-density lithium-ion batteries: bulk or surface degradation? Chem. Mater. 30, 1155–1163 (2018).
Zeng, X., Zhan, C., Lu, J. & Amine, K. Stabilization of a high-capacity and high-power nickel-based cathode for Li-ion batteries. Chem 4, 690–704 (2018).
Jung, R., Metzger, M., Maglia, F., Stinner, C. & Gasteiger, H. A. Oxygen release and its effect on the cycling stability of LiNixMnyCozO2 (NMC) cathode materials for Li-ion batteries. J. Electrochem. Soc. 164, A1361–A1377 (2017).
Li, N. et al. Unraveling the cationic and anionic redox reactions in a conventional layered oxide cathode. ACS Energy Lett. 4, 2836–2842 (2019).
Assat, G. & Tarascon, J. M. Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries. Nat. Energy 3, 373–386 (2018).
Yan, P. et al. Injection of oxygen vacancies in the bulk lattice of layered cathodes. Nat. Nanotechnol. 14, 602–608 (2019).
Yan, P. et al. Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries. Nat. Commun. 8, 14101 (2017).
Lin, F. et al. Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries. Nat. Energy 1, 1–8 (2016).
Lin, F. et al. Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries. Nat. Commun. 5, 3529 (2014).
Sun, H.-H. & Manthiram, A. Impact of microcrack generation and surface degradation on a nickel-rich layered Li[Ni0.9Co0.05Mn0.05]O2 cathode for lithium-ion batteries. Chem. Mater. 29, 8486–8493 (2017).
Gent, W. E. et al. Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides. Nat. Commun. 8, 2091 (2017).
House, R. A. et al. What triggers oxygen loss in oxygen redox cathode materials? Chem. Mater. 31, 3293–3300 (2019).
Lee, W. et al. Advances in the cathode materials for lithium rechargeable batteries. Angew. Chem. Int. Ed. 58, 2–30 (2019).
Chen, C. H. et al. Aluminum-doped lithium nickel cobalt oxide electrodes for high-power lithium-ion batteries. J. Power Sources 128, 278–285 (2004).
We acknowledge support from the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (VTO). This work was also supported by Clean Vehicles, US–China Clean Energy Research Centre (CERC-CVC2) under the US DOE EERE Vehicle Technologies Office. Argonne National Laboratory is operated for the DOE Office of Science by the UChicago Argonne, LLC, under contract no. DE-AC02-06CH11357. This research was partially supported by the National Key R&D Program of China (2016YFB0700600), the Guangdong Innovation Team Project (no. 2013N080), the Soft Science Research Project of Guangdong Province (no. 2017B030301013) and the Shenzhen Science and Technology Research Grants (no. ZDSYS201707281026184). T.L. thanks F.P. for the supervision and consultation on this work during his PhD study. This research used resources of the Advanced Photon Source (11-ID-C and 9-BM), a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract no. DE-AC02-06CH11357. This work was performed including electron microscopy, in part, at the Center for Nanoscale Materials, a US Department of Energy Office of Science User Facility, and supported by the US Department of Energy, Office of Science, under Contract no. DE-AC02-06CH11357.
The authors declare no competing interests.
Peer review information Nature Energy thanks Xinping Ai and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Liu, T., Yu, L., Liu, J. et al. Understanding Co roles towards developing Co-free Ni-rich cathodes for rechargeable batteries. Nat Energy 6, 277–286 (2021). https://doi.org/10.1038/s41560-021-00776-y
Insights into Li‐Rich Mn‐Based Cathode Materials with High Capacity: from Dimension to Lattice to Atom
Advanced Energy Materials (2021)
Nano Letters (2021)