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Fabrication of liquid cell for in situ transmission electron microscopy of electrochemical processes

Nature Protocols volume 18, pages 555–578 (2023)Cite this article

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Abstract

Fundamentally understanding the complex electrochemical reactions that are associated with energy devices (e.g., rechargeable batteries, fuel cells and electrolyzers) has attracted worldwide attention. In situ liquid cell transmission electron microscopy (TEM) offers opportunities to directly observe and analyze in-liquid specimens without the need for freezing or drying, which opens up a door for visualizing these complex electrochemical reactions at the nano scale in real time. The key to the success of this technique lies in the design and fabrication of electrochemical liquid cells with thin but strong imaging windows. This protocol describes the detailed procedures of our established technique for the fabrication of such electrochemical liquid cells (~110 h). In addition, the protocol for the in situ TEM observation of electrochemical reactions by using the nanofabricated electrochemical liquid cell is also presented (2 h). We also show and analyze experimental results relating to the electrochemical reactions captured. We believe that this protocol will shed light on strategies for fabricating high-quality TEM liquid cells for probing dynamic electrochemical reactions in high resolution, providing a powerful research tool. This protocol requires access to a clean room equipped with specialized nanofabrication setups as well as TEM characterization equipment.

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Fig. 1: Electrochemistry liquid cell (E-cell) fabricated by this protocol.
Fig. 2: Flow chart of the fabrication of an electrochemical liquid cell in this protocol.
Fig. 3: Evolution of the E-cell during the fabrication process.
Fig. 4: Schematic illustration of the wafer cross-section at different fabrication stages.
Fig. 5: Assembly of the top chip and bottom chip.
Fig. 6: Operation process for wire bonding, loading liquid electrolyte and incorporating the prepared E-cell on the TEM holder.
Fig. 7: Schematic illustration of the in situ TEM observation and post in situ characterizations.
Fig. 8: In situ TEM observation of the lithium-gold reaction using E-cell I (gold electrode, commercial LiPF6/EC/DEC electrolyte).
Fig. 9: In situ TEM observation of the lithiation and delithiation of MoS2 nanosheets by using E-cell II (titanium/MoS2 electrode, commercial LiPF6/EC/DEC electrolyte).
Fig. 10: In situ TEM observation of sodium electrodeposition on a flat titanium surface by using E-cell III (titanium electrode, commercial NaPF6/PC electrolyte).
Fig. 11: Characterization of the SEI layer on the titanium anode in E-cell II (titanium/MoS2 electrode, commercial LiPF6/EC/DEC electrolyte).

Data availability

The main data supporting the findings of this study were previously published in the supporting primary research papers. Additional imaging data are in the Supplementary Figures or are available from the corresponding author upon reasonable request.

References

  1. Spurgeon, S. R. et al. Towards data-driven next-generation transmission electron microscopy. Nat. Mater. 20, 274–279 (2021).

    Article  CAS  Google Scholar 

  2. de Jonge, N., Houben, L., Dunin-Borkowski, R. E. & Ross, F. M. Resolution and aberration correction in liquid cell transmission electron microscopy. Nat. Rev. Mater. 4, 61–78 (2019).

    Article  Google Scholar 

  3. Nellist, P. D. et al. Direct sub-angstrom imaging of a crystal lattice. Science 305, 1741 (2004).

    Article  CAS  Google Scholar 

  4. Yang, R. et al. High-yield production of mono- or few-layer transition metal dichalcogenide nanosheets by an electrochemical lithium ion intercalation-based exfoliation method. Nat. Protoc. 17, 358–377 (2022).

    Article  CAS  Google Scholar 

  5. Yang, R. et al. MnO2-based materials for environmental applications. Adv. Mater. 33, e2004862 (2021).

    Article  Google Scholar 

  6. Ross Frances, M. Opportunities and challenges in liquid cell electron microscopy. Science 350, aaa9886 (2015).

    Article  CAS  Google Scholar 

  7. de Jonge, N. & Ross, F. M. Electron microscopy of specimens in liquid. Nat. Nanotechnol. 6, 695–704 (2011).

    Article  Google Scholar 

  8. De Yoreo, J. J. & Sommerdijk, N. A. J. M. Investigating materials formation with liquid-phase and cryogenic TEM. Nat. Rev. Mater. 1, 16035 (2016).

    Article  Google Scholar 

  9. Kashin, A. S. & Ananikov, V. P. Monitoring chemical reactions in liquid media using electron microscopy. Nat. Rev. Chem. 3, 624–637 (2019).

    Article  CAS  Google Scholar 

  10. Zeng, Z., Zheng, W. & Zheng, H. Visualization of colloidal nanocrystal formation and electrode–electrolyte interfaces in liquids using TEM. Acc. Chem. Res. 50, 1808–1817 (2017).

    Article  CAS  Google Scholar 

  11. Zheng, H., Meng, Y. S. & Zhu, Y. Frontiers of in situ electron microscopy. MRS Bull. 40, 12–18 (2015).

    Article  Google Scholar 

  12. Zheng, H. et al. Observation of single colloidal platinum nanocrystal growth trajectories. Science 324, 1309–1312 (2009).

    Article  CAS  Google Scholar 

  13. Yuk Jong, M. et al. High-resolution EM of colloidal nanocrystal growth using graphene liquid cells. Science 336, 61–64 (2012).

    Article  Google Scholar 

  14. Liao, H.-G., Cui, L., Whitelam, S. & Zheng, H. Real-time imaging of Pt3Fe nanorod growth in solution. Science 336, 1011–1014 (2012).

    Article  CAS  Google Scholar 

  15. Liao, H.-G. et al. Facet development during platinum nanocube growth. Science 345, 916–919 (2014).

    Article  CAS  Google Scholar 

  16. Yang, J. et al. Formation of two-dimensional transition metal oxide nanosheets with nanoparticles as intermediates. Nat. Mater. 18, 970–976 (2019).

    Article  CAS  Google Scholar 

  17. Li, D. et al. Direction-specific interactions control crystal growth by oriented attachment. Science 336, 1014–1018 (2012).

    Article  CAS  Google Scholar 

  18. Nielsen, M. H., Aloni, S. & De Yoreo, J. J. In situ TEM imaging of CaCO3 nucleation reveals coexistence of direct and indirect pathways. Science 345, 1158–1162 (2014).

    Article  CAS  Google Scholar 

  19. Smeets, P. J. M., Cho, K. R., Kempen, R. G. E., Sommerdijk, N. A. J. M. & De Yoreo, J. J. Calcium carbonate nucleation driven by ion binding in a biomimetic matrix revealed by in situ electron microscopy. Nat. Mater. 14, 394–399 (2015).

    Article  CAS  Google Scholar 

  20. Williamson, M. J., Tromp, R. M., Vereecken, P. M., Hull, R. & Ross, F. M. Dynamic microscopy of nanoscale cluster growth at the solid–liquid interface. Nat. Mater. 2, 532–536 (2003).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  22. Zeng, Z. et al. Visualization of electrode–electrolyte interfaces in LiPF6/EC/DEC electrolyte for lithium ion batteries via in situ TEM. Nano Lett. 14, 1745–1750 (2014).

    Article  CAS  Google Scholar 

  23. Zeng, Z. et al. In situ study of lithiation and delithiation of MoS2 nanosheets using electrochemical liquid cell transmission electron microscopy. Nano Lett. 15, 5214–5220 (2015).

    Article  CAS  Google Scholar 

  24. Zeng, Z., Liang, W.-I., Chu, Y.-H. & Zheng, H. In situ TEM study of the Li–Au reaction in an electrochemical liquid cell. Faraday Discuss. 176, 95–107 (2014).

    Article  CAS  Google Scholar 

  25. Zeng, Z. et al. Electrode roughness dependent electrodeposition of sodium at the nanoscale. Nano Energy 72, 104721 (2020).

    Article  CAS  Google Scholar 

  26. Zhang, Q. et al. In situ TEM visualization of LiF nanosheet formation on the cathode-electrolyte interphase (CEI) in liquid-electrolyte lithium-ion batteries. Matter 5, 1235–1250 (2022).

    Article  CAS  Google Scholar 

  27. Yuan, Y., Amine, K., Lu, J. & Shahbazian-Yassar, R. Understanding materials challenges for rechargeable ion batteries with in situ transmission electron microscopy. Nat. Commun. 8, 15806 (2017).

    Article  CAS  Google Scholar 

  28. Fan, Z. et al. In situ transmission electron microscopy for energy materials and devices. Adv. Mater. 31, e1900608 (2019).

    Article  Google Scholar 

  29. Kushima, A. et al. Charging/discharging nanomorphology asymmetry and rate-dependent capacity degradation in Li–oxygen battery. Nano Lett. 15, 8260–8265 (2015).

    Article  CAS  Google Scholar 

  30. Kushima, A. et al. Liquid cell transmission electron microscopy observation of lithium metal growth and dissolution: root growth, dead lithium and lithium flotsams. Nano Energy 32, 271–279 (2017).

    Article  CAS  Google Scholar 

  31. Beermann, V. et al. Real-time imaging of activation and degradation of carbon supported octahedral Pt–Ni alloy fuel cell catalysts at the nanoscale using in situ electrochemical liquid cell STEM. Energy Environ. Sci. 12, 2476–2485 (2019).

    Article  CAS  Google Scholar 

  32. Kühne, M. et al. Reversible superdense ordering of lithium between two graphene sheets. Nature 564, 234–239 (2018).

    Article  Google Scholar 

  33. Lee, S.-Y. et al. Unveiling the mechanisms of lithium dendrite suppression by cationic polymer film induced solid–electrolyte interphase modification. Energy Environ. Sci. 13, 1832–1842 (2020).

    Article  CAS  Google Scholar 

  34. De Jonge, N., Peckys, D. B., Kremers, G. & Piston, D. Electron microscopy of whole cells in liquid with nanometer resolution. Proc. Natl Acad. Sci. USA 106, 2159–2164 (2009).

    Article  Google Scholar 

  35. Peckys, D. B. & de Jonge, N. Visualizing gold nanoparticle uptake in live cells with liquid scanning transmission electron microscopy. Nano Lett. 11, 1733–1738 (2011).

    Article  CAS  Google Scholar 

  36. Lu, Y. et al. Self-hydrogenated shell promoting photocatalytic H2 evolution on anatase TiO2. Nat. Commun. 9, 2752 (2018).

    Article  Google Scholar 

  37. Yuk, J. M., Seo, H. K., Choi, J. W. & Lee, J. Y. Anisotropic lithiation onset in silicon nanoparticle anode revealed by in situ graphene liquid cell electron microscopy. ACS Nano 8, 7478–7485 (2014).

    Article  CAS  Google Scholar 

  38. Gammer, C., Burak Ozdol, V., Liebscher, C. H. & Minor, A. M. Diffraction contrast imaging using virtual apertures. Ultramicroscopy 155, 1–10 (2015).

    Article  CAS  Google Scholar 

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Acknowledgements

Z.Z. acknowledges the ECS scheme (CityU9048163) from RGC in Hong Kong and Basic Research Project from Shenzhen Science and Technology Innovation Committee in Shenzhen, China (No. JCYJ20210324134012034).

Author information

Authors and Affiliations

  1. Department of Materials Science and Engineering, City University of Hong Kong, Kowloon, Hong Kong, China

    Ruijie Yang, Liang Mei, Yingying Fan, Qingyong Zhang & Zhiyuan Zeng

  2. State Key Lab of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China

    Hong-Gang Liao

  3. School of Chemical Engineering and Technology, Xi’an Jiaotong University, Xi’an, China

    Juan Yang

  4. Department of Nuclear Science and Engineering and Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

    Ju Li

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

    Zhiyuan Zeng

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Contributions

Z.Z. developed the protocol and performed the experiments. R.Y., J.L. and Z.Z. drafted and envisioned the manuscript. L.M., Y.F., Q.Z., H.-G.L. and J.Y. provided some comments on the manuscript. All authors reviewed the manuscript.

Corresponding authors

Correspondence to Ju Li or Zhiyuan Zeng.

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Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Protocols thanks Nicholas Clark and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Related links

Key references using this protocol

Zhang, Q. et al. Matter 5, 1235–1250 (2022): https://doi.org/10.1016/j.matt.2022.01.015

Zeng, Z. et al. Nano Energy 72, 104721 (2020): https://doi.org/10.1016/j.nanoen.2020.104721

Zeng, Z. et al. Nano Lett. 15, 5214–5220 (2015): https://doi.org/10.1021/acs.nanolett.5b02483

Zeng, Z. et al. Faraday Discuss. 176, 95–107 (2014): https://doi.org/10.1039/C4FD00145A

Key data used in this protocol

Zeng, Z. et al. Nano Lett. 14, 1745–1750 (2014): https://doi.org/10.1021/nl403922u

Supplementary information

Supplementary Information

Supplementary Table 1, Supplementary Figures 1–8, Supplementary references

Supplementary Video 1

Fabrication process of the electrochemical liquid cell

Supplementary Video 2

In situ TEM observation of electrochemical processes and post in situ characterizations, which include HAADF-STEM, EDS and 4D-STEM techniques

Supplementary Video 3

Lithiation of MoS2 nanosheets under cyclic voltammetry with an applied voltage range of 3–0 V, showing the reaction and dissolution of MoS2 on a titanium electrode. Reproduced with permission from ref. 23, American Chemical Society.

Supplementary Video 4

Slow growth of SEI film on a titanium electrode under cyclic voltammetry with an applied potential of 0–3 V. Reproduced with permission from ref. 23, American Chemical Society.

Supplementary Video 5

Electrochemical deposition and dissolution of sodium on a flat titanium electrode. Reproduced with permission from ref. 25, Elsevier.

Supplementary Video 6

Electrochemical deposition and dissolution of sodium on a non-flat titanium electrode with nanoscale surface curvature. Reproduced with permission from ref. 25, Elsevier.

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Yang, R., Mei, L., Fan, Y. et al. Fabrication of liquid cell for in situ transmission electron microscopy of electrochemical processes. Nat Protoc 18, 555–578 (2023). https://doi.org/10.1038/s41596-022-00762-y

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  • DOI: https://doi.org/10.1038/s41596-022-00762-y

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