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.

  • Article
  • Published:

Compositionally complex doping for zero-strain zero-cobalt layered cathodes

Nature volume 610, pages 67–73 (2022)Cite this article

Subjects

Abstract

The high volatility of the price of cobalt and the geopolitical limitations of cobalt mining have made the elimination of Co a pressing need for the automotive industry1. Owing to their high energy density and low-cost advantages, high-Ni and low-Co or Co-free (zero-Co) layered cathodes have become the most promising cathodes for next-generation lithium-ion batteries2,3. However, current high-Ni cathode materials, without exception, suffer severely from their intrinsic thermal and chemo-mechanical instabilities and insufficient cycle life. Here, by using a new compositionally complex (high-entropy) doping strategy, we successfully fabricate a high-Ni, zero-Co layered cathode that has extremely high thermal and cycling stability. Combining X-ray diffraction, transmission electron microscopy and nanotomography, we find that the cathode exhibits nearly zero volumetric change over a wide electrochemical window, resulting in greatly reduced lattice defects and local strain-induced cracks. In-situ heating experiments reveal that the thermal stability of the new cathode is significantly improved, reaching the level of the ultra-stable NMC-532. Owing to the considerably increased thermal stability and the zero volumetric change, it exhibits greatly improved capacity retention. This work, by resolving the long-standing safety and stability concerns for high-Ni, zero-Co cathode materials, offers a commercially viable cathode for safe, long-life lithium-ion batteries and a universal strategy for suppressing strain and phase transformation in intercalation electrodes.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

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

Fig. 1: Superior stability of the HE-LNMO cathode.
Fig. 2: Structural and electrochemical characterizations of HE-LNMO layered cathode.
Fig. 3: Cycling stability and local coordinate environment stability of HE-LNMO.
Fig. 4: Structural and mechanical stability of HE-LNMO.

Similar content being viewed by others

Data availability

 Source data are provided with this paper. The data that support the findings of this study are available from the corresponding author (huolin.xin@uci.edu) upon reasonable request.

References

  1. Turcheniuk, K., Bondarev, D., Singhal, V. & Yushin, G. Ten years left to redesign lithium-ion batteries. Nature 559, 467–470 (2018).

    Article  CAS  PubMed  ADS  Google Scholar 

  2. Li, W., Erickson, E. M. & Manthiram, A. High-nickel layered oxide cathodes for lithium-based automotive batteries. Nat. Energy 5, 26–34 (2020).

    Article  CAS  ADS  Google Scholar 

  3. Li, W., Lee, S. & Manthiram, A. High-nickel NMA: a cobalt-free alternative to NMC and NCA cathodes for lithium-ion batteries. Adv. Mater. 32, 2002718 (2020).

    Article  CAS  Google Scholar 

  4. Bi, Y. et al. Reversible planar gliding and microcracking in a single-crystalline Ni-rich cathode. Science 370, 1313–1317 (2020).

    Article  CAS  PubMed  ADS  Google Scholar 

  5. Liu, H. et al. A disordered rock salt anode for fast-charging lithium-ion batteries. Nature 585, 63–67 (2020).

    Article  CAS  PubMed  ADS  Google Scholar 

  6. Lin, R. et al. Anomalous metal segregation in lithium-rich material provides design rules for stable cathode in lithium-ion battery. Nat. Commun. 10, 1650 (2019).

    Article  PubMed  PubMed Central  ADS  Google Scholar 

  7. Manthiram, A. & Goodenough, J. B. Layered lithium cobalt oxide cathodes. Nat. Energy 6, 323–323 (2021).

    Article  CAS  ADS  Google Scholar 

  8. Liu, W. et al. Nickel-rich layered lithium transition-metal oxide for high-energy lithium-ion batteries. Angew. Chem. Int. Edn Engl. 54, 4440–4457 (2015).

    Article  CAS  Google Scholar 

  9. Yan, P. et al. Coupling of electrochemically triggered thermal and mechanical effects to aggravate failure in a layered cathode. Nat. Commun. 9, 2437 (2018).

    Article  PubMed  PubMed Central  ADS  Google Scholar 

  10. 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  CAS  ADS  Google Scholar 

  11. 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. Edn Engl. 58, 10434–10458 (2019).

    Article  CAS  Google Scholar 

  12. Manthiram, A. A reflection on lithium-ion battery cathode chemistry. Nat. Commun. 11, 1550 (2020).

    Article  CAS  PubMed  PubMed Central  ADS  Google Scholar 

  13. Liu, T. et al. Understanding Co roles towards developing Co-free Ni-rich cathodes for rechargeable batteries. Nat. Energy 6, 277–286 (2021).

  14. Li, J. et al. Structural origin of the high-voltage instability of lithium cobalt oxide. Nat. Nanotechnol. 16, 599–605 (2021).

    Article  CAS  PubMed  ADS  Google Scholar 

  15. Mu, L. et al. Dopant distribution in Co-free high-energy layered cathode materials. Chem. Mater. 31, 9769–9776 (2019).

    Article  CAS  Google Scholar 

  16. Mu, L. et al. Structural and electrochemical impacts of Mg/Mn dual dopants on the LiNiO2 cathode in Li-metal batteries. ACS Appl. Mater. Interfaces 12, 12874–12882 (2020).

    Article  CAS  PubMed  Google Scholar 

  17. Sun, H. H. et al. Beyond doping and coating: prospective strategies for stable high-capacity layered Ni-rich cathodes. ACS Energy Lett. 5, 1136–1146 (2020).

    Article  CAS  Google Scholar 

  18. Xie, Q., Li, W. & Manthiram, A. A Mg-doped high-nickel layered oxide cathode enabling safer, high-energy-density Li-ion batteries. Chem. Mater. 31, 938–946 (2019).

    Article  CAS  Google Scholar 

  19. Wang, C. et al. Resolving atomic-scale phase transformation and oxygen loss mechanism in ultrahigh-nickel layered cathodes for cobalt-free lithium-ion batteries. Matter 4, 2013–2026 (2021).

  20. Wang, C., Zhang, R., Kisslinger, K. & Xin, H. L. Atomic-scale observation of O1 faulted phase-induced deactivation of LiNiO2 at high voltage. Nano Lett. 21, 3657–3663 (2021).

    Article  CAS  PubMed  ADS  Google Scholar 

  21. Feng, X., Ren, D., He, X. & Ouyang, M. Mitigating thermal runaway of lithium-ion batteries. Joule 4, 743–770 (2020).

  22. 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).

    Article  CAS  PubMed  PubMed Central  ADS  Google Scholar 

  23. 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).

    Article  CAS  Google Scholar 

  24. Huang, Y. et al. Thermal stability and reactivity of cathode materials for Li-ion batteries. ACS Appl. Mater. Interfaces 8, 7013–7021 (2016).

    Article  CAS  PubMed  Google Scholar 

  25. Yeh, J. W. et al. Nanostructured high-entropy alloys with multiple principal elements: novel alloy design concepts and outcomes. Adv. Eng. Mater. 6, 299–303 (2004).

    Article  CAS  Google Scholar 

  26. Zhao, C., Ding, F., Lu, Y., Chen, L. & Hu, Y. S. High-entropy layered oxide cathodes for sodium-ion batteries. Angew. Chem. Int. Edn Engl. 59, 264–269 (2020).

    Article  CAS  Google Scholar 

  27. Lun, Z. et al. Cation-disordered rocksalt-type high-entropy cathodes for Li-ion batteries. Nat. Mater. 20, 214–221 (2021).

    Article  CAS  PubMed  ADS  Google Scholar 

  28. Wang, J. et al. Lithium containing layered high entropy oxide structures. Sci. Rep. 10, 18430 (2020).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  29. Zou, L. et al. Lattice doping regulated interfacial reactions in cathode for enhanced cycling stability. Nat. Commun. 10, 3447 (2019).

    Article  PubMed  PubMed Central  ADS  Google Scholar 

  30. Bak, S.-M. et al. Structural changes and thermal stability of charged LiNixMnyCozO2 cathode materials studied by combined in situ time-resolved XRD and mass spectroscopy. ACS Appl. Mater. Interfaces 6, 22594–22601 (2014).

    Article  CAS  PubMed  Google Scholar 

  31. Yoon, M. et al. Reactive boride infusion stabilizes Ni-rich cathodes for lithium-ion batteries. Nat. Energy 6, 362–371 (2021).

    Article  CAS  ADS  Google Scholar 

  32. Xu, J. et al. Understanding the degradation mechanism of lithium nickel oxide cathodes for Li-ion batteries. ACS Appl. Mater. Interfaces 8, 31677–31683 (2016).

    Article  CAS  PubMed  Google Scholar 

  33. Tian, C. et al. Charge heterogeneity and surface chemistry in polycrystalline cathode materials. Joule 2, 464–477 (2018).

    Article  CAS  Google Scholar 

  34. Ohzuku, T., Ueda, A. & Yamamoto, N. Zero‐strain insertion material of Li [Li1/3Ti5/3] O4 for rechargeable lithium cells. J. Electrochem. Soc. 142, 1431 (1995).

    Article  CAS  ADS  Google Scholar 

  35. Funke, H., Scheinost, A. C. & Chukalina, M. Wavelet analysis of extended x-ray absorption fine structure data. Phys. Rev. B 71, 094110 (2005).

    Article  ADS  Google Scholar 

  36. Li, L. et al. In X-Ray Nanoimaging: Instruments and Methods III vol. 10389 (eds Somogyi, A. & Lai, B.) https://doi.org/10.1117/12.2272585 (Proc. SPIE, International Society for Optical Engineering, 2017).

  37. Sun, X. et al. New phases and phase transitions observed in over-charged states of LiCoO2-based cathode materials. J. Power Sources 97-98, 274–276 (2001).

    Article  CAS  ADS  Google Scholar 

  38. de Picciotto, L. A., Thackeray, M. M., David, W. I. F., Bruce, P. G. & Goodenough, J. B. Structural characterization of delithiated LiVO2. Mater. Res. Bull. 19, 1497–1506 (1984).

    Article  Google Scholar 

  39. Zhou, Y.-N. et al. Tuning charge–discharge induced unit cell breathing in layer-structured cathode materials for lithium-ion batteries. Nat. Commun. 5, 5381 (2014).

    Article  PubMed  ADS  Google Scholar 

  40. Liu, H. et al. Intergranular cracking as a major cause of long-term capacity fading of layered cathodes. Nano Lett. 17, 3452–3457 (2017).

    Article  CAS  PubMed  ADS  Google Scholar 

  41. Watanabe, S., Kinoshita, M., Hosokawa, T., Morigaki, K. & Nakura, K. Capacity fading of LiAlyNi1−x−yCoxO2 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−x−yCoxO2 particle). J. Power Sources 260, 50–56 (2014).

    Article  CAS  ADS  Google Scholar 

  42. de Biasi, L. et al. Between scylla and charybdis: balancing among structural stability and energy density of layered NCM cathode materials for advanced lithium-ion batteries. J. Phys. Chem. C 121, 26163–26171 (2017).

    Article  Google Scholar 

  43. Cui, Z., Xie, Q. & Manthiram, A. Zinc-doped high-nickel, low-cobalt layered oxide cathodes for high-energy-density lithium-ion batteries. ACS Appl. Mater. Interfaces 13, 15324–15332 (2021).

    Article  CAS  PubMed  Google Scholar 

  44. Lee, S. et al. In-depth analysis of the degradation mechanisms of high-nickel, low/no-cobalt layered oxide cathodes for lithium-ion batteries. Adv. Energy Mater. 11, 2100858 (2021).

    Article  CAS  Google Scholar 

  45. Xie, Q., Cui, Z. & Manthiram, A. Unveiling the stabilities of nickel-based layered oxide cathodes at an identical degree of delithiation in lithium-based batteries. Adv. Mater. 33, 2100804 (2021).

    Article  CAS  Google Scholar 

  46. Zhou, K., Xie, Q., Li, B. & Manthiram, A. An in-depth understanding of the effect of aluminum doping in high-nickel cathodes for lithium-ion batteries. Energy Storage Mater. 34, 229–240 (2021).

    Article  Google Scholar 

  47. Yoon, C. S. et al. High-energy Ni-rich Li[NixCoyMn1–x–y]O2 cathodes via compositional partitioning for next-generation electric vehicles. Chem. Mater. 29, 10436–10445 (2017).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work is primarily supported by the US Department of Energy (DOE)’s Office of Energy Efficiency and Renewable Energy (EERE) under award no. DE-EE0008444. The in situ TEM study of Li deintercalation is supported by US DOE’s Office of Basic Energy Sciences, under award no. DE-SC0021204. The work done by R.Z. for this study was funded by the startup funding of H.L.X. R.L. was supported by the Assistant Secretary for EERE, Vehicle Technology Office of the US DOE through the Advanced Battery Materials Research (BMR) Program, under contract no. DE-SC0012704. The work performed at Pacific Northwest National Laboratory was supported by the US DOE’s Office of EERE through the Applied Battery Research Program under contract no. DE-AC05-76RL01830. This research used the resources of the Center for Functional Nanomaterials as well as 7-BM, 18-ID, 5-ID beamlines of the National Synchrotron Light Source II, which are two US DOE Office of Science facilities, at Brookhaven National Laboratory under contract no. DE-SC0012704. This research used the resources of the Advanced Photon Source, a US DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the US DOE, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515. We acknowledge the use of facilities and instrumentation at the UC Irvine Materials Research Institute, which is supported in part by the National Science Foundation through the UC Irvine Materials Research Science and Engineering Center (no. DMR-2011967). We also acknowledge the electrode produced at the US DOE’s Cell Analysis, Modeling, and Prototyping (CAMP) Facility, Argonne National Laboratory. The CAMP Facility is fully supported by the DOE Vehicle Technologies Office.

Author information

Author notes

  1. These authors contributed equally: Rui Zhang, Chunyang Wang

Authors and Affiliations

  1. Department of Physics and Astronomy, University of California, Irvine, CA, USA

    Rui Zhang, Chunyang Wang, Peichao Zou & Huolin L. Xin

  2. Chemistry Division, Brookhaven National Laboratory, Upton, NY, USA

    Ruoqian Lin

  3. National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, NY, USA

    Lu Ma, Steven N. Ehrlich, Yang Yang, Andrew M. Kiss & Mingyuan Ge

  4. X-ray Science Division, Argonne National Laboratory, Lemont, IL, USA

    Liang Yin, Tianyi Li, Wenqian Xu & Yang Ren

  5. Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA, USA

    Hao Jia, Qiuyan Li & Wu Xu

  6. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Sami Sainio & Sang Jun Lee

  7. Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY, USA

    Kim Kisslinger

  8. Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA

    Stephen E. Trask & Bryant J. Polzin

Authors
  1. Rui Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Chunyang Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Peichao Zou
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Ruoqian Lin
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Lu Ma
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Liang Yin
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Tianyi Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Wenqian Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Hao Jia
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Qiuyan Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Sami Sainio
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Kim Kisslinger
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Stephen E. Trask
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Steven N. Ehrlich
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Yang Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  16. Andrew M. Kiss
    View author publications

    You can also search for this author in PubMed Google Scholar

  17. Mingyuan Ge
    View author publications

    You can also search for this author in PubMed Google Scholar

  18. Bryant J. Polzin
    View author publications

    You can also search for this author in PubMed Google Scholar

  19. Sang Jun Lee
    View author publications

    You can also search for this author in PubMed Google Scholar

  20. Wu Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  21. Yang Ren
    View author publications

    You can also search for this author in PubMed Google Scholar

  22. Huolin L. Xin
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

H.L.X. conceived the idea and directed the project. R.Z. synthesized the materials and performed the electrochemical experiments, soft/hard XAS experiments and data analysis. C.W. performed the in-situ and ex-situ TEM experiments and analyses, and TXM tomography data analyses. P.Z. performed the DSC and TGA–MS experiments. Y.R., L.Y., T.L. and Wenqian Xu performed in-situ and ex-situ XRD experiments. R.L., S.N.E. and L.M. performed the XANES and EXAFS measurements. H.J., Q.L. and Wu Xu prepared electrolytes and helped with the single-layer pouch cell test. M.G. performed the TXM experiments and data analysis. Y.Y. and A.M.K. performed the X-ray fluorescence experiments. S.S. and S.J.L. performed the soft X-ray absorption experiment. K.K. performed the FIB-SEM experiments. B.P. and S.T. fabricated the commercial NMC cathode. C.W., R.Z. and H.L.X. wrote the paper with the help of all authors.

Corresponding author

Correspondence to Huolin L. Xin.

Ethics declarations

Competing interests

H.L.X. reports two US non-provisional patent applications and a PCT application filed by the University of California, Irvine, on the basis of this work.

Peer review

Peer review information

Nature thanks the anonymous reviewers for their contribution to the peer review of this work.

Additional information

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

Extended data figures and tables

Extended Data Fig. 1 In-situ heating low-mag S/TEM and EDS mapping.

a, In-situ heating HAADF-STEM of charged HE-LNMO up to 350 °C. b, In-situ heating TEM of charged NMC-811 up to 350 °C. c, EDS mapping of charged HE-LNMO after heating at 350 °C.

Extended Data Fig. 2 Thermal stability and impedance of NMC-811 and HE-LNMO.

a, Quantified DSC result of charged state NMC-811 and HE-LNMO. Both electrodes are CC+CV charged to 4.4 V at 0.1 C current. b, EIS of LNO, NMC-811, and HE-LNMO under the same cell condition. The result shows that HE-LNMO has the lowest impedance and pure LNO has the largest impedance.

Extended Data Fig. 3 High-temperature cycling performance of NMC-811 and HE-LNMO.

a-b, Galvanostatic charge/discharge curve of HE-LNMO and NMC-811 at 50 °C, C/10. The result shows the initial Columbic efficiency of HE-LNMO (94%) is significantly higher than that of the NMC-811 (85%), indicating much less side reaction in HE-LNMO compared with NMC-811. c, cycling performance of HE-LNMO and NMC-811 at 50 °C, C/2.

Extended Data Fig. 4 FT-EXAFS of transition metals in HE-LNMO and NMC-811 before and after cycling.

a-b, FT-EXAFS of Ni, Mn before and after cycling. The TM-O bonding and TM-TM coordinate in (a) HE-LNMO and (b) NMC-811, respectively. c, FT-EXAFS of Ni, Mn, Ti, Nb and Mo in pristine HE-LNMO. d, FT-EXAFS of Ti, Nb and Mo in pristine and cycled HE-LNMO.

Extended Data Fig. 5 Multi-dimensional structural-stability characterization of NMC-811 and HE-LNMO.

a, Wavelet-transformed Ni-K edge EXAFS of HE-LNMO and NMC-811 during long-term cycling. b–c, Soft X-ray absorption (XAS) of Ni-L3 edge in cycled NMC-811 and HE-LNMO (cutoff 2.5–4.3 V, 1C) at TFY mode (b) and TEY mode (c). d–e, lattice parameters change during long cycling of (d) HE-LNMO and (e) NMC-811 calculated by XRD. f–h, X-ray fluorescence (XRF) mapping result of Ni dissolution on the graphite (Gr) anode. Ni distribution on Gr anode paired with HE-LNMO (f) and NMC-811 (g), respectively (cycling condition: 2.5V–4.4 V vs Gr, 1C; field of view: 0.25mm*0.25mm). h, Quantitative result derived from the data in f and g. i, SAED pattern of pristine HE-LNMO cathode and that after 500th long cycles. j, EDS mapping of long cycled HE-LNMO, showing the stable element distribution during long cycling.

Extended Data Table 1 Capacity vs. Volume change in the state-of-art high-Ni, low-Co and benchmark cathodes
Full size table

Supplementary information

Supplementary Information

Supplementary Figs. 1–19 and Discussion. The additional characterization of HE-LNMO, cycling performance, in-situ and ex-situ cell data and the further validation of the high-entropy doping strategy’s universality are listed.

Source data

Rights and permissions

Springer Nature or its licensor holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, R., Wang, C., Zou, P. et al. Compositionally complex doping for zero-strain zero-cobalt layered cathodes. Nature 610, 67–73 (2022). https://doi.org/10.1038/s41586-022-05115-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41586-022-05115-z

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Advanced 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