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.

Progressive growth of the solid–electrolyte interphase towards the Si anode interior causes capacity fading

Subjects

Abstract

The solid–electrolyte interphase (SEI), a layer formed on the electrode surface, is essential for electrochemical reactions in batteries and critically governs the battery stability. Active materials, especially those with extremely high energy density, such as silicon (Si), often inevitably undergo a large volume swing upon ion insertion and extraction, raising a critical question as to how the SEI interactively responds to and evolves with the material and consequently controls the cycling stability of the battery. Here, by integrating sensitive elemental tomography, an advanced algorithm and cryogenic scanning transmission electron microscopy, we unveil, in three dimensions, a correlated structural and chemical evolution of Si and SEI. Corroborated with a chemomechanical model, we demonstrate progressive electrolyte permeation and SEI growth along the percolation channel of the nanovoids due to vacancy injection and condensation during the delithiation process. Consequently, the Si–SEI spatial configuration evolves from the classic ‘core–shell’ structure in the first few cycles to a ‘plum-pudding’ structure following extended cycling, featuring the engulfing of Si domains by the SEI, which leads to the disruption of electron conduction pathways and formation of dead Si, contributing to capacity loss. The spatially coupled interactive evolution model of SEI and active materials, in principle, applies to a broad class of high-capacity electrode materials, leading to a critical insight for remedying the fading of high-capacity electrodes.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: Experimental set-up, battery performance and structural evolution of Si.
Fig. 2: Cryo-STEM-HAADF image and EDS elemental composition mapping to illustrate the structural and chemical evolution of Si and the SEI upon cycling.
Fig. 3: Cryo-STEM-EDS tomography on 3D structure and elemental distribution of the Si–SEI composite after 36 cycles.
Fig. 4: Segmented viewing of 3D cryo-STEM-EDS chemical composition from two directions to illustrate the spatially correlated evolution of the Si and SEI layer with battery cycles.
Fig. 5: Microstructure-based modelling of the SEI inward growth during lithiation/delithiation cycles.

Data availability

All data that support the findings of this study have been included in the main text, Supplementary Information and Supplementary Videos 1–6. The original data are kept at the Environmental Molecular Sciences Laboratory at Pacific Northwest National Laboratory and are available from the corresponding authors upon request.

References

  1. 1.

    Chen, J. et al. Electrolyte design for LiF-rich solid–electrolyte interfaces to enable high-performance microsized alloy anodes for batteries. Nat. Energy 5, 386–397 (2020).

    CAS  Google Scholar 

  2. 2.

    Wu, H. et al. Stable cycling of double-walled silicon nanotube battery anodes through solid–electrolyte interphase control. Nat. Nanotechnol. 7, 310–315 (2012).

    CAS  Google Scholar 

  3. 3.

    Chan, C. K. et al. High-performance lithium battery anodes using silicon nanowires. Nat. Nanotechnol. 3, 31–35 (2008).

    CAS  Google Scholar 

  4. 4.

    Kim, H., Lee, E.-J. & Sun, Y.-K. Recent advances in the Si-based nanocomposite materials as high capacity anode materials for lithium ion batteries. Mater. Today 17, 285–297 (2014).

    CAS  Google Scholar 

  5. 5.

    Choi, S., Kwon, T. W., Coskun, A. & Choi, J. W. Highly elastic binders integrating polyrotaxanes for silicon microparticle anodes in lithium ion batteries. Science 357, 279–283 (2017).

    CAS  Google Scholar 

  6. 6.

    Li, Y. et al. Growth of conformal graphene cages on micrometre-sized silicon particles as stable battery anodes. Nat. Energy 1, 15029 (2016).

    CAS  Google Scholar 

  7. 7.

    Liu, N. et al. A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes. Nat. Nanotechnol. 9, 187–192 (2014).

    CAS  Google Scholar 

  8. 8.

    An, W. et al. Scalable synthesis of ant-nest-like bulk porous silicon for high-performance lithium-ion battery anodes. Nat. Commun. 10, 1447 (2019).

    Google Scholar 

  9. 9.

    Magansinski, A. et al. High-performance lithium-ion anodes using a hierarchical bottom-up approach. Nat. Mater. 9, 353–358 (2010).

    Google Scholar 

  10. 10.

    Liu, N. et al. A yolk-shell design for stabilized and scalable Li-ion battery alloy anodes. Nano Lett. 12, 3315–3321 (2012).

    CAS  Google Scholar 

  11. 11.

    Lu, Z. et al. Nonfilling carbon coating of porous silicon micrometer-sized particles for high-performance lithium battery anodes. ACS Nano 9, 2540–2547 (2015).

    CAS  Google Scholar 

  12. 12.

    Szczech, J. R. & Jin, S. Nanostructured silicon for high capacity lithium battery anodes. Energy Environ. Sci. 4, 56–72 (2011).

    CAS  Google Scholar 

  13. 13.

    Huang, S., Fan, F., Li, J., Zhang, S. & Zhu, T. Stress generation during lithiation of high-capacity electrode particles in lithium ion batteries. Acta Mater. 61, 4354–4364 (2013).

    CAS  Google Scholar 

  14. 14.

    Kim, H., Han, B., Choo, J. & Cho, J. Three-dimensional porous silicon particles for use in high-performance lithium secondary batteries. Angew. Chem. Int. Ed. 47, 10151–10154 (2008).

    CAS  Google Scholar 

  15. 15.

    Kennedy, T., Brandon, M. & Ryan, K. M. Advances in the application of silicon and germanium nanowires for high-performance lithium-ion batteries. Adv. Mater. 28, 5696–5704 (2016).

    CAS  Google Scholar 

  16. 16.

    Liu, X. H. et al. Size-dependent fracture of silicon nanoparticles during lithiation. ACS Nano 6, 1522–1531 (2011).

    Google Scholar 

  17. 17.

    Zhao, K. et al. Concurrent reaction and plasticity during initial lithiation of crystalline silicon in lithium-ion batteries. J. Electrochem. Soc. 159, A238–A243 (2012).

    CAS  Google Scholar 

  18. 18.

    Gohier, A. et al. High-rate capability silicon decorated vertically aligned carbon nanotubes for Li-ion batteries. Adv. Mater. 24, 2592–2597 (2012).

    CAS  Google Scholar 

  19. 19.

    Yoon, T., Nguyen, C. C., Seo, D. M. & Lucht, B. L. Capacity fading mechanisms of silicon nanoparticle negative electrodes for lithium ion batteries. J. Electrochem. Soc. 162, A2325–A2330 (2015).

    CAS  Google Scholar 

  20. 20.

    Wetjen, M. et al. Morphological changes of silicon nanoparticles and the influence of cutoff potentials in silicon-graphite electrodes. J. Electrochem. Soc. 165, A1503–A1514 (2018).

    CAS  Google Scholar 

  21. 21.

    Chan, C. K., Ruffo, R., Hong, S. S. & Cui, Y. Surface chemistry and morphology of the solid electrolyte interphase on silicon nanowire lithium-ion battery anodes. J. Power Sources 189, 1132–1140 (2009).

    CAS  Google Scholar 

  22. 22.

    Krause, L. J., Brandt, T., Chevrier, V. L. & Jensen, L. D. Surface area increase of silicon alloys in Li-ion full cells measured by isothermal heat flow calorimetry. J. Electrochem. Soc. 164, A2277–A2282 (2017).

    CAS  Google Scholar 

  23. 23.

    Cho, J. H. & Picraux, S. T. Silicon nanowire degradation and stablization during lithium cycling by SEI layer formation. Nano Lett. 14, 3088–3095 (2014).

    CAS  Google Scholar 

  24. 24.

    Zhang, Q. et al. Harnessing the concurrent reaction dynamics in active Si and Ge to achieve high performance lithium-ion batteries. Energy Environ. Sci. 11, 669–681 (2018).

    CAS  Google Scholar 

  25. 25.

    Huang, W. et al. Dynamic structure and chemistry of the silicon solid-electrolyte interphase visualized by cryogenic electron microscopy. Matter 1, 1232–1245 (2019).

    Google Scholar 

  26. 26.

    Midgley, P. A. & Dunin-Borkowski, R. E. Electron tomography and holography in materials science. Nat. Mater. 8, 271–280 (2009).

    CAS  Google Scholar 

  27. 27.

    Zhou, J. et al. Observing crystal nucleation in four dimensions using atomic electron tomography. Nature 570, 500–503 (2019).

    CAS  Google Scholar 

  28. 28.

    Turoňová, B. et al. Benchmarking tomographic acquisition schemes for high-resolution structural biology. Nat. Commun. 11, 876 (2020).

    Google Scholar 

  29. 29.

    Li, Y. et al. Atomic structure of sensitive battery materials and interfaces revealed by cryo-electron microscopy. Science 358, 506–510 (2017).

    CAS  Google Scholar 

  30. 30.

    Wang, X. et al. New insights on the structure of electrochemically deposited lithium metal and its solid electrolyte interphases via cryogenic TEM. Nano Lett. 17, 7606–7612 (2017).

    CAS  Google Scholar 

  31. 31.

    Liu, X. H. et al. Anisotropic swelling and fracture of silicon nanowires during lithiation. Nano Lett. 11, 3312–3318 (2011).

    CAS  Google Scholar 

  32. 32.

    Choi, J. W. et al. Stepwise nanopore evolution in one-dimensional nanostructures. Nano Lett. 10, 1409–1413 (2010).

    CAS  Google Scholar 

  33. 33.

    Chen, Q. & Sieradzki, K. Spontaneous evolution of bicontinuous nanostructures in dealloyed Li-based systems. Nat. Mater. 12, 1102–1106 (2013).

    CAS  Google Scholar 

  34. 34.

    Hu, Y. S. et al. Electrochemical lithiation synthesis of nanoporous materials with superior catalytic and capacitive activity. Nat. Mater. 5, 713–717 (2006).

    CAS  Google Scholar 

  35. 35.

    Wang, A., Kadam, S., Li, H., Shi, S. & Qi, Y. Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries. npj Comput. Mater. 4, 15 (2018).

    Google Scholar 

  36. 36.

    Ploehn, H. J., Ramadass, P. & White, R. E. Solvent diffusion model for aging of lithium-ion battery cells. J. Electrochem. Soc. 151, A456–A462 (2004).

    CAS  Google Scholar 

  37. 37.

    Pharr, M., Zhao, K., Wang, X., Suo, Z. & Vlassak, J. J. Kinetics of initial lithiation of crystalline silicon electrodes of lithium-ion batteries. Nano Lett. 12, 5039–5047 (2012).

    CAS  Google Scholar 

  38. 38.

    Zhang, S. Chemomechanical modeling of lithiation-induced failure in high-volume-change electrode materials for lithium ion batteries. npj Comput. Mater. 3, 7 (2017).

    Google Scholar 

  39. 39.

    Zhu, J. et al. In situ TEM of phosphorus-dopant-induced nanopore formation in delithiated silicon nanowires. ACS Appl. Mater. Interfaces 11, 17313–18320 (2019).

    CAS  Google Scholar 

  40. 40.

    Chen, C. et al. Impact of dual-layer solid-electrolyte interphase inhomogeneities on early-stage defect formation in Si electrodes. Nat. Commun. 11, 3283 (2020).

    CAS  Google Scholar 

  41. 41.

    Zhu, B. et al. Minimized lithium trapping by isovalent isomorphism for high initial Coulombic efficiency of silicon anodes. Sci. Adv. 5, eaax0651 (2019).

    CAS  Google Scholar 

  42. 42.

    Zachman, M. J., Tu, Z., Choudhury, S., Archer, L. A. & Kourkoutis, L. F. Cryo-STEM mapping of solid–liquid interfaces and dendrites in lithium-metal batteries. Nature 560, 345–349 (2018).

    CAS  Google Scholar 

  43. 43.

    Huang, W. et al. Evolution of the solid–electrolyte interphase on carbonaceous anodes visualized by atomic-resolution cryogenic electron microscopy. Nano Lett. 19, 5140–5148 (2019).

    CAS  Google Scholar 

  44. 44.

    Xiao, Q. et al. Inward lithium-ion breathing of hierarchically porous silicon anodes. Nat. Commun. 6, 8844 (2015).

    CAS  Google Scholar 

  45. 45.

    Wang, C. et al. Self-healing chemistry enables the stable operation of silicon microparticle anodes for high-energy lithium-ion batteries. Nat. Chem. 5, 1042–1048 (2013).

    CAS  Google Scholar 

  46. 46.

    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).

    CAS  Google Scholar 

  47. 47.

    Sigworth, F. J., Doerschuk, P. C., Carazo, J.-M. & Scheres, S. H. W. An introduction to maximum-likelihood methods in cryo-EM. Methods Enzymol. 482, 263–294 (2010).

    CAS  Google Scholar 

  48. 48.

    Aarle, W. V. et al. The ASTRA Toolbox: a platform for advanced algorithm development in electron tomography. Ultramicroscopy 157, 35–47 (2015).

    Google Scholar 

  49. 49.

    Chen, L. et al. Modulation of dendritic patterns during electrodeposition: a nonlinear phase-field model. J. Power Sources 300, 376–385 (2015).

    CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy. This work was performed partly at the William R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the US Department of Energy, Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy under contract DE-AC05-76RL01830. The cryo-STEM-EDS tomography was performed at the Hillsboro Nanoport of Thermo Fisher Scientific. We thank R. Warren for his assistance on the tomography data processing. This work was also performed, in part, at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the US Department of Energy, Office of Science. S.Z. acknowledges support by the National Science Foundation (CBET-2034899).

Author information

Affiliations

Authors

Contributions

C.W., J.-G.Z. and X.L. conceived the project. Y.H. and X.L. designed the experiment. J.Y. synthesized the Si nanowire on the stainless-steel anode. H.J. and R.Y. assembled and cycled the coin cells. Y.H. and Y.X. performed the cryo-TEM experiments. Y.H., L.J., A.G., and C.B.-M. conducted the cryo-STEM-EDS tomography experiments under the supervision of L.P. and T.T.; L.J. and M.S. conducted the tomography data reconstruction and visualization. T.C., D.X. and S.Z. carried out the modelling calculation. Y.H., L.J., C.W. and S.Z. draughted the manuscript. All authors contributed to the revision of the manuscript.

Corresponding authors

Correspondence to Jinkyoung Yoo, Xiaolin Li, Sulin Zhang or Chongmin Wang.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature Nanotechnology thanks Peter Ercius and the other, anonymous, reviewer(s) 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. 1–37, Table 1, Discussion, evaluation of electron beam effect and optimization of imaging conditions, additional information about the background and signal intensity, and reference.

Supplementary Video 1

Cryo-STEM-EDS tomography showing 3D structure and elemental distribution of a Si nanowire after the first cycle.

Supplementary Video 2

Cryo-STEM-EDS tomography showing cross-sectional information of a Si nanowire after the first cycle.

Supplementary Video 3

Cryo-STEM-EDS tomography showing 3D structure and elemental distribution of a Si nanowire after the 36th cycle.

Supplementary Video 4

Cryo-STEM-EDS tomography showing cross-sectional information of a Si nanowire after the 36th cycle.

Supplementary Video 5

Cryo-STEM-EDS tomography showing 3D structure and elemental distribution of a Si nanowire after the 100th cycle.

Supplementary Video 6

Cryo-STEM-EDS tomography showing cross-sectional information of a Si nanowire after the 100th cycle.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

He, Y., Jiang, L., Chen, T. et al. Progressive growth of the solid–electrolyte interphase towards the Si anode interior causes capacity fading. Nat. Nanotechnol. 16, 1113–1120 (2021). https://doi.org/10.1038/s41565-021-00947-8

Download citation

Search

Quick links

Find nanotechnology articles, nanomaterial data and patents all in one place. Visit Nano by Nature Research