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.

Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging

Nature Energy volume 3, pages 641–647 (2018)Cite this article

Subjects

Abstract

Lithium-rich layered oxides (LRLO) are among the leading candidates for the next-generation cathode material for energy storage, delivering 50% excess capacity over commercially used compounds. Despite excellent prospects, voltage fade has prevented effective use of the excess capacity, and a major challenge has been a lack of understanding of the mechanisms underpinning the voltage fade. Here, using operando three-dimensional Bragg coherent diffractive imaging, we directly observe the nucleation of a mobile dislocation network in LRLO nanoparticles. The dislocations form more readily in LRLO as compared with a classical layered oxide, suggesting a link between the defects and voltage fade. We show microscopically how the formation of partial dislocations contributes to the voltage fade. The insights allow us to design and demonstrate an effective method to recover the original high-voltage functionality. Our findings reveal that the voltage fade in LRLO is reversible and call for new paradigms for improved design of oxygen-redox active materials.

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

Relevant articles

Open Access articles citing this article.

Access options

Rent or buy this article

Get just this article for as long as you need it

$39.95

Learn more

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

Fig. 1: Formation of a dislocation network during charge.
Fig. 2: In situ evolution of a LRLO nanoparticle during electrochemical charge.
Fig. 3: In situ evolution of a NCA nanoparticle during charge.
Fig. 4: Strain energy landscape of single particles of layered oxides.
Fig. 5: A path to restore the voltage in the lithium-rich oxide material.

References

  1. Lee, J. et al. Unlocking the potential of cation-disordered oxides for rechargeable lithium batteries. Science 343, 519–522 (2014).

    Article  Google Scholar 

  2. Sathiya, M. et al. Reversible anionic redox chemistry in high-capacity layered-oxide electrodes. Nat. Mater. 12, 827–835 (2013).

    Article  Google Scholar 

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

    Article  Google Scholar 

  4. Nitta, N., Wu, F., Lee, J. T. & Yushin, G. Li-ion battery materials: present and future. Mater. Today 18, 252–264 (2015).

    Article  Google Scholar 

  5. 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 

  6. 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).

    Article  Google Scholar 

  7. Delmas, C. Battery materials: Operating through oxygen. Nat. Chem. 8, 641–643 (2016).

    Article  Google Scholar 

  8. Renfrew, S. E. & McCloskey, B. D. Residual lithium carbonate predominantly accounts for first cycle CO2 and CO outgassing of Li-stoichiometric and Li-rich layered transition-metal oxides. J. Am. Chem. Soc. 139, 17853–17860 (2017).

    Article  Google Scholar 

  9. 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 (2011).

    Article  Google Scholar 

  10. Hy, S., Felix, F., Rick, J., Su, W.-N. & Hwang, B. J. Direct in situ observation of Li2O evolution on Li-rich high-capacity cathode material, Li[NixLi(1−2x)/3Mn(2−x)/3]O2 (0 ≤ x ≤ 0.5). J. Am. Chem. Soc. 136, 999–1007 (2014).

    Article  Google Scholar 

  11. 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 

  12. Ye, D. et al. Understanding the origin of Li2MnO3 activation in Li-rich cathode materials for lithium-ion batteries. Adv. Funct. Mater. 25, 7488–7496 (2015).

    Article  Google Scholar 

  13. Seymour, I. D. et al. Characterizing oxygen local environments in paramagnetic battery materials via 17O NMR and DFT calculations. J. Am. Chem. Soc. 138, 9405–9408 (2016).

    Article  Google Scholar 

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

    Article  Google Scholar 

  15. 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).

    Article  Google Scholar 

  16. 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 

  17. Liu, H. et al. Operando lithium dynamics in the Li-rich layered oxide cathode material via neutron diffraction. Adv. Energy Mater. 6, 1502143 (2016).

    Article  Google Scholar 

  18. Chen, C.-J. et al. The origin of capacity fade in the Li2MnO3·LiMO2 (M = Li, Ni, Co, Mn) microsphere positive electrode: An operando neutron diffraction and transmission X-ray microscopy study. J. Am. Chem. Soc. 138, 8824–8833 (2016).

    Article  Google Scholar 

  19. Wang, H., Jang, Y. I. & Huang, B. TEM study of electrochemical cycling‐induced damage and disorder in LiCoO2 cathodes for rechargeable lithium batteries. J. Electrochem. Soc. 146, 473–480 (1999).

    Article  Google Scholar 

  20. Watanabe, S., Kinoshita, M., Hosokawa, T., Morigaki, K. & Nakura, K. Capacity fade of LiAlyNi1−x−yCoxO2 cathode for lithium-ion batteries during accelerated calendar and cycle life tests (surface analysis of LiAlyNi1−x−yCoxO2 cathode after cycle tests in restricted depth of discharge ranges). J. Power Sources 258, 210–217 (2014).

    Article  Google Scholar 

  21. Gent, W. E. et al. Persistent state-of-charge heterogeneity in relaxed, partially charged Li1−xNi1/3Co1/3Mn 1/3O2 secondary particles. Adv. Mater. 28, 6631–6638 (2016).

    Article  Google Scholar 

  22. Gabrisch, H., Yazami, R. & Fultz, B. The character of dislocations in LiCoO. Electrochem. Solid-State Lett. 5, A111 (2002).

    Article  Google Scholar 

  23. Huang, J. Y. et al. In situ observation of the electrochemical lithiation of a single SnO2 nanowire electrode. Science 330, 1515–1520 (2010).

    Article  Google Scholar 

  24. Ulvestad, A. et al. Topological defect dynamics in operando battery nanoparticles. Science 348, 1344–1347 (2015).

    Article  Google Scholar 

  25. 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  Google Scholar 

  26. Pfeifer, M. A., Williams, G. J., Vartanyants, I. A., Harder, R. & Robinson, I. K. Three-dimensional mapping of a deformation field inside a nanocrystal. Nature 442, 63–66 (2006).

    Article  Google Scholar 

  27. Clark, J. N. et al. Three-dimensional imaging of dislocation propagation during crystal growth and dissolution. Nat. Mater. 14, 780–784 (2015).

    Article  Google Scholar 

  28. Takahashi, Y. et al. Bragg X-ray ptychography of a silicon crystal: Visualization of the dislocation strain field and the production of a vortex beam. Phys. Rev. B 87, 121201 (2013).

    Article  Google Scholar 

  29. Nye, J. F. & Berry, M. V. Dislocations in wave trains. Proc. R. Soc. A 336, 165–190 (1974).

    Article  MathSciNet  MATH  Google Scholar 

  30. Hull, D. & Bacon, D. J. Introduction to Dislocations 5th edn. (Elsevier, Oxford, 2011).

  31. Qi, Y., Hector, L. G., James, C. & Kim, K. J. Lithium concentration dependent elastic properties of battery electrode materials from first principles calculations. J. Electrochem. Soc. 161, F3010–F3018 (2014).

    Article  Google Scholar 

  32. Yu, H. et al. Electrochemical kinetics of the 0.5Li2MnO3·0.5LiMn0.42Ni0.42Co0.16O2 ‘composite’ layered cathode material for lithium-ion batteries. RSC Adv. 2, 8797–8807 (2012).

    Article  Google Scholar 

  33. Fell, C. R. et al. High pressure driven structural and electrochemical modifications in layered lithium transition metal intercalation oxides. Energy Environ. Sci. 5, 6214–6224 (2012).

    Article  Google Scholar 

  34. 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).

    Article  Google Scholar 

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

    Google Scholar 

  36. Poirer, J.-P. Creep of Crystals (Cambridge Univ. Press, Cambridge, 2005).

  37. Sun, L., Marrocchelli, D. & Yildiz, B. Edge dislocation slows down oxide ion diffusion in doped CeO2 by segregation of charged defects. Nat. Commun. 6, 6294 (2015).

    Article  Google Scholar 

  38. Szot, K., Speier, W., Bihlmayer, G. & Waser, R. Switching the electrical resistance of individual dislocations in single-crystalline SrTiO3. Nat. Mater. 5, 312–320 (2006).

    Article  Google Scholar 

  39. Waser, R., Dittmann, R., Staikov, G. & Szot, K. Redox-based resistive switching memories - Nanoionic mechanisms, prospects, and challenges. Adv. Mater. 21, 2632–2663 (2009).

    Article  Google Scholar 

  40. Singer, A. et al. Nonequilibrium structural dynamics of nanoparticles in LiNi1/2Mn3/2O4 cathode under operando conditions. Nano Lett. 14, 5295–5300 (2014).

    Article  Google Scholar 

  41. Elser, V. Phase retrieval by iterated projections. J. Opt. Soc. Am. A 20, 40–55 (2003).

    Article  Google Scholar 

  42. Luke, D. R. Relaxed averaged alternating reflections for diffraction imaging. Inverse Probl. 21, 37–50 (2005).

    Article  MathSciNet  MATH  Google Scholar 

  43. Williamson, G. K. & Hall, W. H. X-ray line broadening from filed aluminium and wolfram. Acta Metall. 1, 22–31 (1953).

    Article  Google Scholar 

  44. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

    Article  Google Scholar 

  45. Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

    Article  Google Scholar 

  46. Perdew, J. P. J., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Article  Google Scholar 

  47. Robertson, A. D. & Bruce, P. G. Mechanism of electrochemical activity in Li2MnO3. Chem. Mater. 15, 1984–1992 (2003).

    Article  Google Scholar 

Download references

Acknowledgements

We acknowledge K. Wiaderek for providing the potentiostat during the measurements at the Advanced Photon Source and H. Liu and K. Chapman for collecting the ex situ powder diffraction data on the NCA material. We also thank A. Van der Ven and M. Radin for discussions. The X-ray imaging was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, under contract DE-SC0001805 (A.S., D.C., J.W., N.H. and O.G.S.). S.H., C.F., M.Z., H.L. and Y.S.M. acknowledge support on the materials synthesis, electrochemical and materials characterization from the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award no. DE-SC0012583. The sample exchanges and collaborations between UCSD and NIMTE are made possible with the support from Office of Vehicle Technology of the U.S. DOE under the Advanced Battery Materials Research (BMR) Program. This research used resources of the Advanced Photon Source, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. We thank the staff at Argonne National Laboratory and the Advanced Photon Source for their support. Parts of this research were carried out at the light source PETRA III at DESY, a member of the Helmholtz Association (HGF). The data are stored at Sector 34-ID-C of the Advanced Photon Source and at PETRA III at DESY.

Author information

Author notes

  1. A. Singer

    Present address: Cornell University, Ithaca, New York, USA

  2. A. V. Zozulya

    Present address: European XFEL GmbH, Schenefeld, Germany

Authors and Affiliations

  1. Department of Physics, University of California-San Diego, La Jolla, California, USA

    A. Singer, D. Cela, N. Hua, J. Wingert & O. G. Shpyrko

  2. Department of NanoEngineering, University of California-San Diego, La Jolla, California, USA

    M. Zhang, S. Hy, C. Fang, T. A. Wynn, H. Liu & Y. S. Meng

  3. Ningbo Institute of Materials Technology and Engineering (NIMTE), Chinese Academy of Sciences, Zhejiang, China

    B. Qiu, Y. Xia & Z. Liu

  4. Materials Science Division, Argonne National Laboratory, Argonne, Illinois, USA

    A. Ulvestad

  5. Deutsches Elektronen-Synchrotron DESY, Hamburg, Germany

    M. Sprung & A. V. Zozulya

  6. X-ray Science Division, Advanced Photon Source, Argonne, Illinois, USA

    E. Maxey & R. Harder

Authors
  1. A. Singer
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. S. Hy
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. D. Cela
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. C. Fang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. T. A. Wynn
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. B. Qiu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Y. Xia
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Z. Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. A. Ulvestad
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. N. Hua
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. J. Wingert
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. H. Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. M. Sprung
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. A. V. Zozulya
    View author publications

    You can also search for this author in PubMed Google Scholar

  16. E. Maxey
    View author publications

    You can also search for this author in PubMed Google Scholar

  17. R. Harder
    View author publications

    You can also search for this author in PubMed Google Scholar

  18. Y. S. Meng
    View author publications

    You can also search for this author in PubMed Google Scholar

  19. O. G. Shpyrko
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

A.S., S.H., Y.S.M. and O.G.S. conceived the idea; A.S., S.H., D.C., C.F., A.U. and J.W. conducted the imaging experiments on LRLO nanoparticles, with assistance from E.M and R.H.; A.S. and N.H. performed the imaging experiments on NCA nanoparticles, with assistance from A.Z. and M.S.; S.H., C.F. and H.L. prepared the LRLO and NCA samples and performed the materials characterization and electrochemistry testing; A.S. analysed the imaging experiments with help from D.C. and O.G.S.; M.Z. performed the microstrain analysis with help from Y.S.M.; B.Q, Y.X. and Z.L. performed the superstructure restoration and subsequent electrochemistry testing; M.Z., T.W. and Y.S.M. performed the theoretical calculations; E.M. designed the sample environment. A.S. wrote the paper with input from all authors.

Corresponding authors

Correspondence to Y. S. Meng or O. G. Shpyrko.

Ethics declarations

Competing interests

The authors declare no competing interests.

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 Figures 1–15 and Supplementary Table 1

Supplementary Video 1

A 3D representation of the displacement field inside the nanoparticle at 4.0 V state of charge. False colours as in Fig. 2a

Supplementary Video 2

A 3D representation of the displacement field inside the nanoparticle at 4.3 V state of charge. False colours as in Fig. 2a

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Singer, A., Zhang, M., Hy, S. et al. Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging. Nat Energy 3, 641–647 (2018). https://doi.org/10.1038/s41560-018-0184-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41560-018-0184-2

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