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:

A Li-rich layered oxide cathode with negligible voltage decay

Nature Energy volume 8, pages 1078–1087 (2023)Cite this article

Subjects

Abstract

With high capacity at low cost, Li- and Mn-rich (LMR) layered oxides are a promising class of cathodes for next-generation Li-ion batteries. However, substantial voltage decay during cycling, due to the unstable Li2MnO3 honeycomb structure, is still an obstacle to their practical deployment. Here we report a Co-free LMR Li-ion battery cathode with negligible voltage decay. The material has a composite structure consisting of layered LiTMO2 and various stacked Li2MnO3 components, where transition metal (TM) ions that reside in the Li layers of Li2MnO3 form caps to strengthen the stability of the honeycomb structure. This capped-honeycomb structure is persistent after high-voltage cycling and prevents TM migration and oxygen loss as shown by experimental and computational results. This work demonstrates that the long-standing voltage decay problem in LMRs can be effectively mitigated by internally pinning the honeycomb structure, which opens an avenue to developing next-generation high-energy cathode materials.

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: Electrochemical performances of the designed CH-LMR cathode.
Fig. 2: Structure of the prepared CH-LMR.
Fig. 3: First-principles calculation of Li and TM in O2-MnO3 and the associated effect on oxygen stability.
Fig. 4: In situ measurement.
Fig. 5: Change of layer stacking sequence from P2 to O2 (or O4) during the ion-exchange procedure.

Similar content being viewed by others

Data availability

All data supporting the findings in this study are available within the paper and the Supplementary Information. Source data are provided with this paper.

References

  1. Goodenough, J. B. & Park, K.-S. The Li-ion rechargeable battery: a perspective. J. Am. Chem. Soc. 135, 1167–1176 (2013).

    Article  Google Scholar 

  2. Lu, Z., Beaulieu, L. Y., Donaberger, R. A., Thomas, C. L. & Dahn, J. R. Synthesis structure, and electrochemical behavior of Li[NixLi1/3−2x/3Mn2/3−x/3]O2. J. Electrochem. Soc. 149, A778–A791 (2002).

    Article  Google Scholar 

  3. Thackeray, M. M., Johnson, C. S., Vaughey, J. T., Li, N. & Hackney, S. A. Advances in manganese-oxide ‘composite’ electrodes for lithium-ion batteries. J. Mater. Chem. 15, 2257–2267 (2005).

    Article  Google Scholar 

  4. Wen, B. et al. Surface reduction in lithium- and manganese-rich layered cathodes for lithium ion batteries drives voltage decay. J. Mater. Chem. A 10, 21941–21954 (2022).

    Article  Google Scholar 

  5. Shunmugasundaram, R., Senthil Arumugam, R. & Dahn, J. R. High capacity Li-rich positive electrode materials with reduced first-cycle irreversible capacity loss. Chem. Mater. 27, 757–767 (2015).

    Article  Google Scholar 

  6. Zheng, J. et al. Li‐ and Mn‐rich cathode materials: challenges to commercialization. Adv. Energy Mater. 7, 1601284 (2017).

    Article  Google Scholar 

  7. Zhang, J. et al. Addressing voltage decay in Li-rich cathodes by broadening the gap between metallic and anionic bands. Nat. Commun. 12, 3071 (2021).

    Article  Google Scholar 

  8. Cai, M. et al. Stalling oxygen evolution in high-voltage cathodes by lanthurization. Nat. Energy 8, 159–168 (2023).

    Article  Google Scholar 

  9. Rinkel, B. L. D., Vivek, J. P., Garcia-Araez, N. & Grey, C. P. Two electrolyte decomposition pathways at nickel-rich cathode surfaces in lithium-ion batteries. Energy Environ. Sci. 15, 3416–3438 (2022).

    Article  Google Scholar 

  10. Assat, G. & Tarascon, J.-M. Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries. Nat. Energy 3, 373–386 (2018).

    Article  Google Scholar 

  11. Wu, J. et al. Suppression of voltage-decay in Li2MnO3 cathode via reconstruction of layered-spinel coexisting phases. J. Mater. Chem. A 8, 18687–18697 (2020).

    Article  Google Scholar 

  12. Seo, D.-H. et al. The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials. Nat. Chem. 8, 692–697 (2016).

    Article  Google Scholar 

  13. House, R. A. et al. First-cycle voltage hysteresis in Li-rich 3d cathodes associated with molecular O2 trapped in the bulk. Nat. Energy 5, 777–785 (2020).

    Article  Google Scholar 

  14. McCalla, E. et al. Visualization of O–O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries. Science 350, 1516–1521 (2015).

    Article  Google Scholar 

  15. Hong, J. et al. Metal-oxygen decoordination stabilizes anion redox in Li-rich oxides. Nat. Mater. 18, 256–265 (2019).

    Article  Google Scholar 

  16. Xu, J. et al. Elucidating anionic oxygen activity in lithium-rich layered oxides. Nat. Commun. 9, 947 (2018).

    Article  Google Scholar 

  17. 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).

    Article  Google Scholar 

  18. Liu, T. et al. Origin of structural degradation in Li-rich layered oxide cathode. Nature 606, 305–312 (2022).

    Article  Google Scholar 

  19. Hu, S. et al. Insight of a phase compatible surface coating for long‐durable Li‐rich layered oxide cathode. Adv. Energy Mater. 9, 1901795 (2019).

    Article  Google Scholar 

  20. Kim, S. Y. et al. Inhibiting oxygen release from Li‐rich, Mn‐rich layered oxides at the surface with a solution processable oxygen scavenger polymer. Adv. Energy Mater. 11, 2100552 (2021).

    Article  Google Scholar 

  21. Nayak, P. K. et al. Al doping for mitigating the capacity fading and voltage decay of layered Li and Mn-rich cathodes for Li-ion batteries. Adv. Energy Mater. 6, 1502398 (2016).

    Article  Google Scholar 

  22. Liu, W. et al. Countering voltage decay and capacity fading of lithium-rich cathode material at 60 °C by hybrid surface protection layers. Adv. Energy Mater. 5, 1500274 (2015).

    Article  Google Scholar 

  23. Zhu, Z. et al. Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment. Nat. Energy 4, 1049–1058 (2019).

    Article  Google Scholar 

  24. Qiu, B. et al. Gas–solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries. Nat. Commun. 7, 12108 (2016).

    Article  Google Scholar 

  25. Eum, D. et al. Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes. Nat. Mater. 19, 419–427 (2020).

    Article  Google Scholar 

  26. Luo, K. et al. One-pot synthesis of lithium-rich cathode material with hierarchical morphology. Nano Lett. 16, 7503–7508 (2016).

    Article  Google Scholar 

  27. Kim, D. et al. Composite ‘layered-layered-spinel’ cathode structures for lithium-ion batteries. J. Electrochem. Soc. 160, A31–A38 (2013).

    Article  Google Scholar 

  28. Ning, F. et al. Inhibition of oxygen dimerization by local symmetry tuning in Li-rich layered oxides for improved stability. Nat. Commun. 11, 4973 (2020).

    Article  Google Scholar 

  29. Song, J. et al. A high-performance Li–Mn–O Li-rich cathode material with rhombohedral symmetry via intralayer Li/Mn disordering. Adv. Mater. 32, e2000190 (2020).

    Article  Google Scholar 

  30. Li, M. & Lu, J. Cobalt in lithium-ion batteries. Science 367, 979–980 (2020).

    Article  Google Scholar 

  31. Lee, S. & Manthiram, A. Can cobalt be eliminated from lithium-ion batteries? ACS Energy Lett. 7, 3058–3063 (2022).

    Article  Google Scholar 

  32. Zhao, H. et al. Cobalt‐free cathode materials: families and their prospects. Adv. Energy Mater. 12, 2103894 (2022).

    Article  Google Scholar 

  33. Boivin, E. et al. The role of Ni and Co in suppressing O‐loss in Li‐rich layered cathodes. Adv. Funct. Mater. 31, 2003660 (2020).

    Article  Google Scholar 

  34. Lin, T. et al. Faster activation and slower capacity/voltage fading: a bifunctional urea treatment on lithium‐rich cathode materials. Adv. Funct. Mater. 30, 1909192 (2020).

    Article  Google Scholar 

  35. 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).

    Article  Google Scholar 

  36. Dixon, D., Mangold, S., Knapp, M., Ehrenberg, H. & Bhaskar, A. Direct observation of reductive coupling mechanism between oxygen and iron/nickel in cobalt‐free Li‐rich cathode material: an in operando X‐ray absorption spectroscopy study. Adv. Energy Mater. 11, 2100479 (2021).

    Article  Google Scholar 

  37. Kuppan, S., Shukla, A. K., Membreno, D., Nordlund, D. & Chen, G. Revealing anisotropic spinel formation on pristine Li‐ and Mn‐rich layered oxide surface and its impact on cathode performance. Adv. Energy Mater. 7, 1602010 (2017).

    Article  Google Scholar 

  38. Delmas, C., Fouassier, C. & Hagenmuller, P. Structural classification and properties of the layered oxides. Phys. B+C. 99, 81–85 (1980).

    Article  Google Scholar 

  39. Zuo, Y. et al. A high-capacity O2-type Li-rich cathode material with a single-layer Li2MnO3 superstructure. Adv. Mater. 30, e1707255 (2018).

    Article  Google Scholar 

  40. Paulsen, J. M., Thomas, C. L. & Dahn, J. R. Layered Li–Mn‐oxide with the O2 structure: a cathode material for Li‐ion cells which does not convert to spinel. J. Electrochem. Soc. 146, 3560–3565 (1999).

    Article  Google Scholar 

  41. Mohanty, D. et al. Unraveling the voltage-fade mechanism in high-energy-density lithium-ion batteries: origin of the tetrahedral cations for spinel conversion. Chem. Mater. 26, 6272–6280 (2014).

    Article  Google Scholar 

  42. Liu, H. et al. What triggers the voltage hysteresis variation beyond the first cycle in Li-rich 3d layered oxides with reversible cation migration? J. Phys. Chem. Lett. 12, 8740–8748 (2021).

    Article  Google Scholar 

  43. Liu, S. et al. Li–Ti cation mixing enhanced structural and performance stability of Li‐rich layered oxide. Adv. Energy Mater. 9, 1901530 (2019).

    Article  Google Scholar 

  44. Ben Yahia, M., Vergnet, J., Saubanère, M. & Doublet, M.-L. Unified picture of anionic redox in Li/Na-ion batteries. Nat. Mater. 18, 496–502 (2019).

    Article  Google Scholar 

  45. Ha, M. et al. Al‐doping driven suppression of capacity and voltage fadings in 4d‐element containing Li‐ion‐battery cathode materials: machine learning and density functional theory. Adv. Energy Mater. 12, 2201497 (2022).

    Article  Google Scholar 

  46. Yin, L. et al. Operando X-ray diffraction studies of the Mg-ion migration mechanisms in spinel cathodes for rechargeable Mg-ion batteries. J. Am. Chem. Soc. 143, 10649–10658 (2021).

    Article  Google Scholar 

  47. Lin, F. et al. Synchrotron X-ray analytical techniques for studying materials electrochemistry in rechargeable batteries. Chem. Rev. 117, 13123–13186 (2017).

    Article  Google Scholar 

  48. Lu, Z. & Dahn, J. R. Understanding the anomalous capacity of Li/Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 cells using in situ X-ray diffraction and electrochemical studies. J. Electrochem. Soc. 149, A815–A822 (2002).

    Article  Google Scholar 

  49. Castel, E., Berg, E. J., El Kazzi, M., Novák, P. & Villevieille, C. Differential electrochemical mass spectrometry study of the interface of xLi2MnO3·(1 − x)LiMO2 (M = Ni, Co, and Mn) material as a positive electrode in Li-ion batteries. Chem. Mater. 26, 5051–5057 (2014).

    Article  Google Scholar 

  50. Reed, J. & Ceder, G. Role of electronic structure in the susceptibility of metastable transition-metal oxide structures to transformation. Chem. Rev. 104, 4513–4534 (2004).

    Article  Google Scholar 

  51. Liu, H. et al. A radially accessible tubular in situ X-ray cell for spatially resolved operando scattering and spectroscopic studies of electrochemical energy storage devices. J. Appl. Crystallogr. 49, 1665–1673 (2016).

    Article  Google Scholar 

  52. Hammersley, A. FIT2D: a multi-purpose data reduction, analysis and visualization program. J. Appl. Crystallogr. 49, 646–652 (2016).

    Article  Google Scholar 

  53. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    Article  Google Scholar 

  54. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865 (1996).

    Article  Google Scholar 

  55. Dudarev, S., Botton, G., Savrasov, S., Humphreys, C. & Sutton, A. Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA+U study. Phys. Rev. B 57, 1505 (1998).

    Article  Google Scholar 

  56. Wang, L., Maxisch, T. & Ceder, G. Oxidation energies of transition metal oxides within the GGA+U framework. Phys. Rev. B 73, 195107 (2006).

    Article  Google Scholar 

  57. Jain, A. et al. A high-throughput infrastructure for density functional theory calculations. Comput. Mater. Sci. 50, 2295–2310 (2011).

    Article  Google Scholar 

Download references

Acknowledgements

We acknowledge the financial support by National Key R&D Program of China (2020YFA0406203), the Shenzhen Science and Technology Program (Project No. JCYJ20220818101016034, SGDX2019081623240948), the General Research Fund (GRF) scheme (CityU 11220322), CityU 9610533 and the Shenzhen Research Institute, City University of Hong Kong. We thank X. Zhong and N. Wang for providing consultation on the STEM results. Y.X. and C.M.W. acknowledge support from the Toyota Research Institute through the Accelerated Materials Design and Discovery programme and the National Science Foundation through the MRSEC programme (NSF-DMR 1720139) at the Materials Research Center. We acknowledge the computing resources provided by (1) Quest High-Performance Computing Facility at Northwestern University, which is jointly supported by the Office of the Provost, the Office for Research and Northwestern University Information Technology and (2) Bridges-2 at Pittsburgh Supercomputing Center through allocations dmr160027p and mat220007p from the Advanced Cyber-infrastructure Coordination Ecosystem: Services & Support (ACCESS) programme, which is supported by National Science Foundation grants 2138259, 2138286, 2138307, 2137603 and 2138296. Y.X. was also supported by Portland State University Lab Setup Fund. This research also used resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract number DE-AC02-06CH11357.

Author information

Author notes

  1. These authors contributed equally: Dong Luo, He Zhu, Yi Xia, Zijia Yin.

Authors and Affiliations

  1. Department of Physics, City University of Hong Kong, Hong Kong, China

    Dong Luo, He Zhu, Zijia Yin, Yalan Huang, Tingting Yang, Yu Tang, Yang Ren & Qi Liu

  2. Department of Materials Science and Engineering, Northwestern University, Evanston, IL, USA

    Yi Xia & Christopher M. Wolverton

  3. Department of Mechanical and Materials Engineering, Portland State University, Portland, OR, USA

    Yi Xia

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

    Yan Qin & Wenquan Lu

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

    Tianyi Li & Kamila M. Wiaderek

  6. Beijing National Laboratory for Condensed Matter Physics, Chinese Academy of Sciences, Beijing, China

    Qinghua Zhang

  7. Department of Materials Science and Engineering, Tsinghua University, Beijing, China

    Lin Gu

  8. School of Materials and Energy, Electron Microscopy Centre of Lanzhou University and Key Laboratory of Magnetism and Magnetic Materials of the Ministry of Education, Lanzhou University, Lanzhou, China

    Yong Peng & Junwei Zhang

  9. Shenzhen Research Institute, City University of Hong Kong, Shenzhen, China

    Si Lan, Yang Ren & Qi Liu

  10. Centre for Neutron Scattering, City University of Hong Kong, Hong Kong, China

    Qi Liu

  11. Hong Kong Institute for Clean Energy, City University of Hong Kong, Hong Kong, China

    Qi Liu

Authors
  1. Dong Luo
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. He Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yi Xia
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Zijia Yin
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yan Qin
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Tianyi Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Qinghua Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Lin Gu
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Yong Peng
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Junwei Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Kamila M. Wiaderek
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Yalan Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Tingting Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Yu Tang
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Si Lan
    View author publications

    You can also search for this author in PubMed Google Scholar

  16. Yang Ren
    View author publications

    You can also search for this author in PubMed Google Scholar

  17. Wenquan Lu
    View author publications

    You can also search for this author in PubMed Google Scholar

  18. Christopher M. Wolverton
    View author publications

    You can also search for this author in PubMed Google Scholar

  19. Qi Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Q.L. and Y.R. conceived the ideas and designed all the experiments. Q.L., Y.R., W.L. and C.M.W. supervised the project. D.L. and Z.Y. performed the materials synthesis and the ex situ characterizations, including the XRD, ICP and SEM experiments. Y.Q. and W.L. performed the materials evaluation and electrochemical characterization. Y.H., T.Y., Y.T. and S.L. contributed to discussions and interpretation of the electrochemical data. Q.Z., L.G., Y.P. and J.Z. acquired the STEM and HAADF images. H.Z., Y.R., T.L. and K.M.W. carried out the in situ synchrotron characterizations. H.Z., Z.Y. and Y.R. analysed and interpreted the synchrotron XRD data. D.L. performed the in situ DEMS experiments. Y.X. and C.W. performed the first-principles calculations. H.Z., D.L., Q.L., Y.R., Y.X. and Z.Y. wrote the paper. All authors discussed the results and reviewed the paper.

Corresponding authors

Correspondence to Yang Ren, Wenquan Lu, Christopher M. Wolverton or Qi Liu.

Ethics declarations

Competing interests

For Q.L., D.L., H.Z., Y.R. and Z.Y., a US provisional patent application, patent number 63/377, 386, has been filed for this work. The patent is related to the specific material reported in this work and submitted by City University of Hong Kong. All other authors declare no competing interests.

Peer review

Peer review information

Nature Energy thanks Richard Schmuch, Ethan Self and Aditya Singh 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.

Supplementary information

Supplementary Information

Supplementary Figs. 1–13 and Table 1.

Source data

Source Data Fig. 1

Statistical source data.

Source Data Fig. 2

Statistical source data.

Source Data Fig. 3

Statistical source data.

Source Data Fig. 4

Statistical source data.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) 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

Luo, D., Zhu, H., Xia, Y. et al. A Li-rich layered oxide cathode with negligible voltage decay. Nat Energy 8, 1078–1087 (2023). https://doi.org/10.1038/s41560-023-01289-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41560-023-01289-6

This article is cited by

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