journal article·2021-02-18Open access

Understanding Co roles towards developing Co-free Ni-rich cathodes for rechargeable batteries

Tongchao Liu, Lei Yu, Jiajie Liu, Jun Lu, Xuanxuan Bi, Alvin Dai, Matthew Li, Maofan Li, Zongxiang Hu, Lu Ma, Duan Luo, Jiaxin Zheng, Tianpin Wu, Yang Ren, Jianguo Wen, Feng Pan, Khalil Amine

Nature Energy· Volume 6· Issue 3

Abstract

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. Reduction on cobalt reliance is an urgent requirement in the development of sustainable cathode materials for Li-ion batteries. Here the authors analyse the roles of cobalt and its interplay with other ions in high-nickel layered oxides, and deduce a material formula for promising cobalt-free cathodes.
Source: openaire · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: Advancements in Battery Materials · Advanced Battery Materials and Technologies · Advanced Battery Technologies Research

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (40)

Show source-provided references
1. 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).10.1002/aenm.201903864 ↗
2. Li, H. et al. Is cobalt needed in Ni-rich positive electrode materials for lithium ion batteries? J. Electrochem. Soc. 166, A429–A439 (2019).10.1149/2.1381902jes ↗
3. 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).10.1016/j.joule.2017.08.019 ↗
4. Bessette, S. et al. Nanoscale lithium quantification in LixNiyCowMnzO2 as cathode for rechargeable batteries. Sci. Rep. 8, 1–9 (2018).10.1038/s41598-018-33608-3 ↗
5. 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).10.1038/s41560-019-0409-z ↗
6. 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).10.1039/C8EE00001H ↗
7. Li, M. & Lu, J. Cobalt in lithium-ion batteries. Science 367, 979–980 (2020).10.1126/science.aba9168 ↗
8. 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).10.1038/s41560-018-0207-z ↗
9. Liu, T. et al. Correlation between manganese dissolution and dynamic phase stability in spinel-based lithium-ion battery. Nat. Commun. 10, 4721 (2019).10.1038/s41467-019-12626-3 ↗
10. 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).10.1016/j.jpowsour.2020.228579 ↗
11. Lee, J. et al. Unlocking the potential of cation-disordered oxides for rechargeable lithium batteries. Science 343, 519–522 (2014).10.1126/science.1246432 ↗
12. Liu, C., Neale, Z. G. & Cao, G. Understanding electrochemical potentials of cathode materials in rechargeable batteries. Mater. Today 19, 109–123 (2016).10.1016/j.mattod.2015.10.009 ↗
13. Schipper, F. et al. Review—recent advances and remaining challenges for lithium ion battery cathodes. J. Electrochem. Soc. 164, A6220–A6228 (2016).10.1149/2.0351701jes ↗
14. 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).10.1038/s41560-018-0191-3 ↗
15. 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).10.1039/D0TA06375D ↗
16. 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).10.1021/acs.nanolett.9b04452 ↗
17. 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).10.1016/j.nanoen.2018.04.020 ↗
18. 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).10.1002/advs.201600262 ↗
19. Zheng, J. et al. Ni/Li disordering in layered transition metal oxide: electrochemical impact, origin, and control. Acc. Chem. Res. 52, 2201–2209 (2019).10.1021/acs.accounts.9b00033 ↗
20. 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).
21. 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).10.1002/aenm.201601266 ↗
22. 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).10.1039/C6TA08448F ↗
23. 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).10.1039/C8TA10553G ↗
24. 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).10.1021/jacs.8b06150 ↗
25. 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).10.1126/science.1122152 ↗
26. 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).10.1149/2.0381813jes ↗
27. 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).10.1021/acs.chemmater.7b05269 ↗
28. 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).10.1016/j.chempr.2017.12.027 ↗
29. 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).10.1149/2.0021707jes ↗
30. Li, N. et al. Unraveling the cationic and anionic redox reactions in a conventional layered oxide cathode. ACS Energy Lett. 4, 2836–2842 (2019).10.1021/acsenergylett.9b02147 ↗
31. Assat, G. & Tarascon, J. M. Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries. Nat. Energy 3, 373–386 (2018).10.1038/s41560-018-0097-0 ↗
32. Yan, P. et al. Injection of oxygen vacancies in the bulk lattice of layered cathodes. Nat. Nanotechnol. 14, 602–608 (2019).10.1038/s41565-019-0428-8 ↗
33. 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).10.1038/ncomms14101 ↗
34. Lin, F. et al. Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries. Nat. Energy 1, 1–8 (2016).
35. Lin, F. et al. Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries. Nat. Commun. 5, 3529 (2014).10.1038/ncomms4529 ↗
36. 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).10.1021/acs.chemmater.7b03268 ↗
37. 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).10.1038/s41467-017-02041-x ↗
38. House, R. A. et al. What triggers oxygen loss in oxygen redox cathode materials? Chem. Mater. 31, 3293–3300 (2019).10.1021/acs.chemmater.9b00227 ↗
39. Lee, W. et al. Advances in the cathode materials for lithium rechargeable batteries. Angew. Chem. Int. Ed. 58, 2–30 (2019).10.1002/anie.201813331 ↗
40. 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).10.1016/j.jpowsour.2003.10.009 ↗