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

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.

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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

Authors

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 (2022). https://doi.org/10.1038/s41596-022-00762-y

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