CaltechAUTHORS
Published October 19, 2022 | Version Published
Journal Article Open

Molecular understanding of interphase formation via operando polymerization on lithium metal anode

Creators

  • 1. ROR icon University of Science and Technology of China
  • 2. ROR icon Helmholtz-Zentrum Berlin für Materialien und Energie
  • 3. ROR icon Soochow University
  • 4. ROR icon Suzhou Institute of Nano-tech and Nano-bionics
  • 5. ROR icon Shanghai Jiao Tong University
  • 6. ROR icon California Institute of Technology
  • 7. ROR icon University of Potsdam
  • 8. ROR icon United States Army Research Laboratory

Abstract

The stable cycling of lithium electrode has been significantly impeded by the lack of comprehensive and in-depth understanding of the complicated chemistry and unclear formation/evolution mechanisms of solid-electrolyte interphase (SEI). Here we report the formation mechanism of an operando polymerized SEI at the Li/electrolyte interface in an ether electrolyte and its dynamic evolution during the lithium growth process. The polymerization process is initiated by the consumption of the polymerization inhibitor LiNO₃ with the formation of inorganic lithium salts at the Li-electrolyte interface, followed by instantaneous ring-opening polymerization of the cyclic ether solvent triggered by the initiator FSO₂NSO₂• radical, leading to the formation of a polymeric-inorganic composite SEI. The resulted SEI exhibits excellent mechanical flexibility and self-healing property that can effectively accommodate more than 100 times' swelling of lithium during growth by stretching and thinning itself from ∼100 nm to 7 nm, achieving an ultrahigh Coulombic efficiency (99.73%) for lithium plating/stripping.

Additional Information

Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) S.J. and R.C. acknowledge support by the National Key Research and Development Program of China under Grant No. 2017YFA0206700, the National Natural Science Foundation of China (Grant Nos. 52072358 and 51902304), the Anhui Provincial Natural Science Foundation (Grant No. 1908085ME122), and the Fundamental Research Funds for the Central Universities (Grant No. Wk2060140026). The authors thank H. Sun, F. Peng, and Y. Liu from Bruker for the help with in situ AFM and Nano-IR experiments. We thank Infrared Spectroscopy and Micro-spectroscopy Station (BL01B) of National Synchrotron Radiation Laboratory (Hefei, China) for synchrotron FTIR experiments. We appreciate Vacuum Interconnected Nanotech Workstation (Nano-X), Suzhou Institute of Nano-Tech and Nano-Bionics, and the Chinese Academy of Sciences (Suzhou, China) for TOF-SIMS and XPS tests. Y.X. acknowledges financial support from the Alexander von Humboldt Foundation for a Humboldt Fellowship for Postdoctoral Researchers. Y. Lu thanks the Joint Lab for Structural Research at the Integrative Research Institute for the Sciences (IRIS Adlershof).

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Additional details

Identifiers

Eprint ID
118936
Resolver ID
CaltechAUTHORS:20230125-514560000.14

Funding

National Key Research and Development Program of China
2017YFA0206700
National Natural Science Foundation of China
52072358
National Natural Science Foundation of China
51902304
Anhui Provincial Natural Science Foundation
1908085ME122
Fundamental Research Funds for the Central Universities
Wk2060140026
Alexander von Humboldt Foundation
Joint Lab for Structural Research at the Integrative Research Institute for the Sciences (IRIS Adlershof)

Dates

Created
2023-03-29
Created from EPrint's datestamp field
Updated
2023-06-08
Created from EPrint's last_modified field

Caltech Custom Metadata

Other Numbering System Name
WAG
Other Numbering System Identifier
1498