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.

Persistent and partially mobile oxygen vacancies in Li-rich layered oxides

Abstract

Increasing the energy density of layered oxide battery electrodes is challenging as accessing high states of delithiation often triggers voltage degradation and oxygen release. Here we utilize transmission-based X-ray absorption spectromicroscopy and ptychography on mechanically cross-sectioned Li1.18–xNi0.21Mn0.53Co0.08O2–δ electrodes to quantitatively profile the oxygen deficiency over cycling at the nanoscale. The oxygen deficiency penetrates into the bulk of individual primary particles (~200 nm) and is well-described by oxygen vacancy diffusion. Using an array of characterization techniques, we demonstrate that, surprisingly, bulk oxygen vacancies that persist within the native layered phase are indeed responsible for the observed spectroscopic changes. We additionally show that the arrangement of primary particles within secondary particles (~5 μm) causes considerable heterogeneity in the extent of oxygen release between primary particles. Our work merges an ensemble of length-spanning characterization methods and informs promising approaches to mitigate the deleterious effects of oxygen release in lithium-ion battery electrodes.

This is a preview of subscription content

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

All prices are NET prices.

Fig. 1: Electrochemical voltage depression linked to cation disordering and TM reduction.
Fig. 2: Spatial dependence of the Mn oxidation state within primary particles.
Fig. 3: Structural consequences of oxygen release.
Fig. 4: Oxidation state heterogeneity on the secondary particle scale.
Fig. 5: Oxidation state heterogeneity in the charged state.

Data availability

Data supporting the main text figures can be found at https://doi.org/10.5281/zenodo.4697951. Data supporting the Supplementary Information figures can be found at https://doi.org/10.5281/zenodo.4697955.

References

  1. Croy, J. R., Balasubramanian, M., Gallagher, K. G. & Burrell, A. K. Review of the US Department of Energy’s ‘deep dive’ effort to understand voltage fade in Li- and Mn-rich cathodes. Acc. Chem. Res. 48, 2813–2821 (2015).

    Google Scholar 

  2. 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).

    Google Scholar 

  3. Sathiya, M. et al. Origin of voltage decay in high-capacity layered oxide electrodes. Nat. Mater. 14, 230–238 (2015).

    Google Scholar 

  4. Abdellahi, A., Urban, A., Dacek, S. & Ceder, G. The effect of cation disorder on the average Li intercalation voltage of transition-metal oxides. Chem. Mater. 28, 3659–3665 (2016).

    Google Scholar 

  5. Kleiner, K. et al. Origin of high capacity and poor cycling stability of Li-rich layered oxides—a long-duration in situ synchrotron powder diffraction study. Chem. Mater. 30, 3656–3667 (2018).

    Google Scholar 

  6. 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).

    Google Scholar 

  7. Liu, H. et al. Unraveling the rapid performance decay of layered high-energy cathodes: from nanoscale degradation to drastic bulk evolution. ACS Nano 12, 2708–2718 (2018).

    Google Scholar 

  8. 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).

    Google Scholar 

  9. Strehle, B. et al. The role of oxygen release from Li- and Mn-rich layered oxides during the first cycles investigated by on-line electrochemical mass spectrometry. J. Electrochem. Soc. 164, A400–A406 (2017).

    Google Scholar 

  10. Hong, J. et al. Critical role of oxygen evolved from layered Li-excess metal oxides in lithium rechargeable batteries. Chem. Mater. 24, 2692–2697 (2012).

    Google Scholar 

  11. Yan, P. et al. Injection of oxygen vacancies in the bulk lattice of layered cathodes. Nat. Nanotechnol. 14, 602–608 (2019).

    Google Scholar 

  12. 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).

    Google Scholar 

  13. Wang, C. & Zhang, J. Structural and chemical evolution of Li- and Mn-rich layered cathode material. Chem. Mater. 27, 1381–1390 (2015).

    Google Scholar 

  14. 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).

    Google Scholar 

  15. Gu, M. et al. Formation of the spinel phase in the layered composite cathode used in Li-ion batteries. ACS Nano 7, 760–767 (2013).

    Google Scholar 

  16. Teufl, T., Strehle, B., Müller, P., Gasteiger, H. A. & Mendez, M. A. Oxygen release and surface degradation of Li- and Mn-rich layered oxides in variation of the Li2MnO3 content. J. Electrochem. Soc. 165, A2718–A2731 (2018).

    Google Scholar 

  17. Qian, D., Xu, B., Chi, M. & Meng, Y. S. Uncovering the roles of oxygen vacancies in cation migration in lithium excess layered oxides. Phys. Chem. Chem. Phys. 16, 14665–14668 (2014).

    Google Scholar 

  18. Mohanty, D. et al. Correlating cation ordering and voltage fade in a lithium–manganese-rich lithium-ion battery cathode oxide: a joint magnetic susceptibility and TEM study. Phys. Chem. Chem. Phys. 15, 19496–19509 (2013).

    Google Scholar 

  19. Boulineau, A., Simonin, L., Colin, J. F., Bourbon, C. & Patoux, S. First evidence of manganese-nickel segregation and densification upon cycling in Li-rich layered oxides for lithium batteries. Nano Lett. 13, 3857–3863 (2013).

    Google Scholar 

  20. Koga, H. et al. Reversible oxygen participation to the redox processes revealed for Li1.20Mn0.54Co0.13Ni0.13O2. J. Electrochem. Soc. 160, A786–A792 (2013).

    Google Scholar 

  21. Koga, H. et al. Different oxygen redox participation for bulk and surface: a possible global explanation for the cycling mechanism of Li1.20Mn0.54Co0.13Ni0.13O2. J. Power Sources 236, 250–258 (2013).

    Google Scholar 

  22. Gallagher, K. G. et al. Correlating hysteresis and voltage fade in lithium- and manganese-rich layered transition-metal oxide electrodes. Electrochem. Commun. 33, 96–98 (2013).

    Google Scholar 

  23. Dau, H., Liebisch, P. & Haumann, M. X-ray absorption spectroscopy to analyze nuclear geometry and electronic structure of biological metal centers—potential and questions examined with special focus on the tetra-nuclear manganese complex of oxygenic photosynthesis. Anal. Bioanal. Chem. 376, 562–583 (2003).

    Google Scholar 

  24. Yabuuchi, N., Yoshii, K., Myung, S.-T., Nakai, I. & Komaba, S. Detailed studies of a high-capacity electrode material for rechargeable batteries, Li2MnO3−LiCo1/3Ni1/3Mn1/3O2. J. Am. Chem. Soc. 133, 4404–4419 (2011).

    Google Scholar 

  25. Luo, K. et al. Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen. Nat. Chem. 8, 684–691 (2016).

    Google Scholar 

  26. Lee, J. et al. Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials. Nat. Commun. 8, 981 (2017).

    Google Scholar 

  27. Bluhm, H. et al. Soft X-ray microscopy and spectroscopy at the molecular environmental science beamline at the Advanced Light Source. J. Electron Spectros. Relat. Phenom. 150, 86–104 (2006).

    Google Scholar 

  28. Celestre, R. et al. Nanosurveyor 2: A compact Instrument for nano-tomography at the Advanced Light Source. J. Phys. Conf. Ser. 849, 6–10 (2017).

    Google Scholar 

  29. Yu, Y. S. et al. Dependence on crystal size of the nanoscale chemical phase distribution and fracture in LixFePO4. Nano Lett. 15, 4282–4288 (2015).

    Google Scholar 

  30. Shapiro, D. A. et al. Chemical composition mapping with nanometre resolution by soft X-ray microscopy. Nat. Photon. 8, 765–769 (2014).

    Google Scholar 

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

    Google Scholar 

  32. Yang, F. et al. Nanoscale morphological and chemical changes of high voltage lithium–manganese rich NMC composite cathodes with cycling. Nano Lett. 14, 4334–4341 (2014).

    Google Scholar 

  33. Genevois, C. et al. Insight into the atomic structure of cycled lithium-rich layered oxide Li1.20Mn0.54Co0.13Ni0.13O2 using HAADF STEM and electron nanodiffraction. J. Phys. Chem. C 119, 75–83 (2015).

    Google Scholar 

  34. Li, J., Shunmugasundaram, R., Doig, R. & Dahn, J. R. In situ X-ray diffraction study of layered Li–Ni–Mn–Co oxides: effect of particle size and structural stability of core–shell materials. Chem. Mater. 28, 162–171 (2016).

    Google Scholar 

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

    Google Scholar 

  36. 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).

    Google Scholar 

  37. Nemudry, A., Goldberg, E. L., Aguirre, M. & Alario-Franco, M. Á. Electrochemical topotactic oxidation of nonstoichiometric perovskites at ambient temperature. Solid State Sci. 4, 677–690 (2002).

    Google Scholar 

  38. Mefford, J. T. et al. Water electrolysis on La1–xSrxCoO3–δ perovskite electrocatalysts. Nat. Commun. 7, 11053 (2016).

    Google Scholar 

  39. Mefford, J. T., Hardin, W. G., Dai, S., Johnston, K. P. & Stevenson, K. J. Anion charge storage through oxygen intercalation in LaMnO3 perovskite pseudocapacitor electrodes. Nat. Mater. 13, 726–732 (2014).

    Google Scholar 

  40. Kudo, T., Obayashi, H. & Gejo, T. Electrochemical behavior of the perovskite-type Nd1–xSrxCoO3 in an aqueous alkaline solution. J. Electrochem. Soc. 122, 159–163 (1975).

    Google Scholar 

  41. 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).

    Google Scholar 

  42. Lee, E. & Persson, K. A. Structural and chemical evolution of the layered Li-excess LixMnO3 as a function of Li content from first-principles calculations. Adv. Energy Mater. 4, 1400498 (2014).

    Google Scholar 

  43. Gerbig, O., Merkle, R. & Maier, J. Electrical transport and oxygen exchange in the superoxides of potassium, rubidium, and cesium. Adv. Funct. Mater. 25, 2552–2563 (2015).

    Google Scholar 

  44. Royer, S., Duprez, D. & Kaliaguine, S. Oxygen mobility in LaCoO3 perovskites. Catal. Today 112, 99–102 (2006).

    Google Scholar 

  45. Singer, A. et al. Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging. Nat. Energy 3, 641–647 (2018).

    Google Scholar 

  46. Tran, N. et al. Mechanisms associated with the ‘plateau’ observed at high voltage for the overlithiated Li1.12(Ni0.425Mn0.425Co0.15)0.88O2 system. Chem. Mater. 20, 4815–4825 (2008).

    Google Scholar 

  47. Armstrong, A. R. et al. Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2. J. Am. Chem. Soc. 128, 8694–8698 (2006).

    Google Scholar 

  48. Wu, Y. & Manthiram, A. Effect of surface modifications on the layered solid solution cathodes (1 – z) Li[Li1/3Mn2/3]O2 – (z) Li[Mn0.5–yNi0.5–yCo2y]O2. Solid State Ion. 180, 50–56 (2009).

    Google Scholar 

  49. Yin, W. et al. Structural evolution at the oxidative and reductive limits in the first electrochemical cycle of Li1.2Ni0.13Mn0.54Co0.13O2. Nat. Commun. 11, 1252 (2020).

    Google Scholar 

  50. Zhang, Z. et al. Cathode–electrolyte interphase in lithium batteries revealed by cryogenic electron microscopy. Matter 4, 302–312 (2021).

    Google Scholar 

  51. 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).

    Google Scholar 

  52. Qiu, B. et al. Metastability and reversibility of anionic redox-based cathode for high-energy rechargeable batteries. Cell Rep. Phys. Sci. 1, 100028 (2020).

    Google Scholar 

  53. Xu, B., Fell, C. R., Chi, M. & Meng, Y. S. Identifying surface structural changes in layered Li-excess nickel manganese oxides in high voltage lithium ion batteries: a joint experimental and theoretical study. Energy Environ. Sci. 4, 2223–2233 (2011).

    Google Scholar 

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

    Google Scholar 

  55. Fell, C. R. et al. Correlation between oxygen vacancy, microstrain, and cation distribution in lithium-excess layered oxides during the first electrochemical cycle. Chem. Mater. 25, 1621–1629 (2013).

    Google Scholar 

  56. Zheng, J. et al. Functioning mechanism of AlF3 coating on the Li- and Mn-rich cathode materials. Chem. Mater. 26, 6320–6327 (2014).

    Google Scholar 

  57. Mohanty, D. et al. Modification of Ni-rich FCG NMC and NCA cathodes by atomic layer deposition: preventing surface phase transitions for high-voltage lithium-ion batteries. Sci. Rep. 6, 26532 (2016).

    Google Scholar 

  58. Mortemard de Boisse, B. et al. Highly reversible oxygen-redox chemistry at 4.1 V in Na4/7−x[1/7Mn6/7]O2 (: Mn vacancy). Adv. Energy Mater. 8, 1800409 (2018).

    Google Scholar 

  59. Eum, D. et al. Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes. Nat. Mater. 19, 419–428 (2020).

    Google Scholar 

  60. Maitra, U. et al. Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2. Nat. Chem. 10, 288–295 (2018).

    Google Scholar 

  61. House, R. A. et al. Superstructure control of first-cycle voltage hysteresis in oxygen-redox cathodes. Nature 577, 502–508 (2019).

    Google Scholar 

  62. Gent, W. E. et al. Persistent state-of-charge heterogeneity in relaxed, partially charged Li1−xNi1/3Co1/3Mn1/3O2 secondary particles. Adv. Mater. 28, 6631–6638 (2016).

    Google Scholar 

  63. Liu, J. et al. Electrochemical performance studies of Li-rich cathode materials with different primary particle sizes. J. Power Sources 251, 208–214 (2014).

    Google Scholar 

  64. Ruess, R. et al. Influence of NCM particle cracking on kinetics of lithium-ion batteries with liquid or solid electrolyte. J. Electrochem. Soc. 167, 100532 (2020).

    Google Scholar 

  65. 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).

    Google Scholar 

  66. Assat, G., Iadecola, A., Foix, D., Dedryvère, R. & Tarascon, J.-M. Direct quantification of anionic redox over long cycling of Li-rich NMC via hard X-ray photoemission spectroscopy. ACS Energy Lett. 3, 2721–2728 (2018).

    Google Scholar 

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

    Google Scholar 

  68. Kim, S., Cho, W., Zhang, X., Oshima, Y. & Choi, J. W. A stable lithium-rich surface structure for lithium-rich layered cathode materials. Nat. Commun. 7, 13598 (2016).

    Google Scholar 

  69. Lu, Z. & Dahn, J. R. In situ X-ray diffraction study of P2-Na2/3[Ni1/3Mn2/3]O2. J. Electrochem. Soc. 148, A1225 (2001).

    Google Scholar 

  70. Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12, 537–541 (2005).

    Google Scholar 

  71. Dai, K. et al. High reversibility of lattice oxygen redox quantified by direct bulk probes of both anionic and cationic redox reactions. Joule 3, 518–541 (2018).

    Google Scholar 

Download references

Acknowledgements

The battery component of this work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies, Battery Materials Research Program, US Department of Energy (DOE), and by Samsung Advanced Institute of Technology Global Research Outreach program. STXM and X-ray ptychography development was supported by the DOE, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering (contract DE-AC02-76SF00515). This research used resources of the ALS, a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. This work was partially supported by STROBE, a National Science Foundation Science and Technology Center under award DMR1548924. Use of the SSRL, SLAC National Accelerator Laboratory, is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. Part of this work was performed at the Stanford Nano Shared Facilities, supported by the National Science Foundation under award ECCS-1542152. P.M.C. acknowledges support through the Stanford Graduate Fellowship as a Winston and Fu-Mei Chen fellow and through the National Science Foundation Graduate Research Fellowship under Grant no. DGE-1656518. W.E.G. was supported additionally by the ALS Doctoral Fellowship. Y.L. and R.S. acknowledge the financial support from the Toyota Research Institute—Accelerated Materials Design and Discovery (TRI-AMDD) program (Stanford University). We thank L. Echávez, L. Schelhas, T. Mefford, M. Lattimer and B. Enders for helpful discussions and/or experimental support. We acknowledge R. Chin for performing the FIB electrode cross-sectioning for the TEM experiments. We also acknowledge R. Kim for experimental TEM support and helpful discussions.

Author information

Authors and Affiliations

Authors

Contributions

P.M.C., S.S.K., W.E.G., D.A.S., M.F.T. and W.C.C. conceived the study. S.S.K. and E.K. performed the ultramicrotomy sectioning. P.M.C., S.S.K., W.E.G., Y.-S.Y. and D.A.S. collected ex situ STXM and ptychography images and analysed the data. P.M.C., K.L. and K.H.S. collected the SXRD data. P.M.C. collected the neutron diffraction data. P.M.C., K.L., K.H.S. and M.F.T. analysed the diffraction data. S.-J.A. synthesized the material and cycled the mini-18650 cells. P.M.C. performed the ICP-MS, scanning electron microscopy and pycnometry experiments. P.M.C. collected TM K-edge spectra and K.L., W.E.G. and M.F.T. contributed to the interpretation. P.M.C. and W.C.C. developed the diffusion and two-phase core–shell models used. Y.L. and X.X. collected TEM images. Y.L., X.X., P.M.C., A.F.M., R.S. and W.C.C. analysed the TEM data. P.M.C, W.C.C. and M.F.T. wrote the manuscript and all the authors revised the manuscript.

Corresponding authors

Correspondence to David A. Shapiro, Michael F. Toney or William C. Chueh.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature Energy thanks the anonymous reviewers 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.

Supplementary information

Supplementary Information

Supplementary Figs. 1–54, Tables 1–12, Notes 1–9 and Methods.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Csernica, P.M., Kalirai, S.S., Gent, W.E. et al. Persistent and partially mobile oxygen vacancies in Li-rich layered oxides. Nat Energy 6, 642–652 (2021). https://doi.org/10.1038/s41560-021-00832-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41560-021-00832-7

Further reading

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