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A salt-philic, solvent-phobic interfacial coating design for lithium metal electrodes

Nature Energy volume 8, pages 577–585 (2023)Cite this article

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Abstract

A key challenge to enable Li metal batteries as next-generation energy storage devices is to stabilize the interface between the Li metal and the electrolyte. A promising strategy is to promote the formation of a salt-derived robust and stable solid electrolyte interphase (SEI). Here we report a salt-philic, solvent-phobic (SP2) polymer coating for Li metal electrode that selectively transports salt over solvent and thus promotes salt-derived SEI formation. Unlike previously reported artificial SEIs, this SP2 coating approach resulted in enhanced cycling performance in several types of solvent, such as ether, carbonate and fluorinated ether. Specifically, the SP2 coating further enhanced the cycle life of a recently reported high-performance fluorinated ether electrolyte to give a ~400 cycle life (50 µm Li, 2.5 mAh cm−2 nickel manganese cobalt oxide and 80% capacity retention). Our coating design concept can be further fine tuned as promising electrolytes become available.

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Fig. 1: Design concept of the SP2 coating.
Fig. 2: Characterization of the salt philicity and the solvent phobicity of polymers and side chains.
Fig. 3: Selectivity of PyTFSI and SP2perF polymers.
Fig. 4: Electrochemical characterization of SP2perF with different electrolytes.
Fig. 5: Cycling of SP2perF coated Li in Li | |NMC cells.

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The datasets analysed and generated during the current study are included in the paper and its Supplementary Information file. Source data are provided with this paper.

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Acknowledgements

We acknowledge support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy under the Battery Materials Research (BMR) Program and the Battery 500 Consortium. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-1542152. Z.H. acknowledges support from the American Association of University Women international fellowship.

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Author notes

  1. These authors contributed equally: Zhuojun Huang, Jian-Cheng Lai.

Authors and Affiliations

  1. Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA

    Zhuojun Huang, Xin Gao, Yufei Yang & Yi Cui

  2. Department of Chemical Engineering, Stanford University, Stanford, CA, USA

    Zhuojun Huang, Jian-Cheng Lai, Sheng-Lun Liao, Zhiao Yu, Yuelang Chen, Weilai Yu, Huaxin Gong, Jian Qin & Zhenan Bao

  3. Department of Chemistry, Stanford University, Stanford, CA, USA

    Zhiao Yu & Yuelang Chen

  4. Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Yi Cui

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Contributions

Z.H., Y. Cui and Z.B. conceived the idea. J.-C.L. designed and synthesized related polymers. Z.H. designed and conducted material characterizations and electrochemical measurements. S.-L.L. performed the DFT calculations. Z.Y. helped with the materials characterization and provided the FDMB electrolyte. H.G. and W.Y. conducted the XPS characterization. Y. Chen performed the NMR. X.G. contributed to the H-cell experiment design. J.Q. contributed to the data discussion. All authors discussed and analysed the data. Z.H., J.-C.L., Y. Cui and Z.B. wrote and revised the paper.

Corresponding authors

Correspondence to Yi Cui or Zhenan Bao.

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Competing interests

For Z.H., J.-C.L., Y. Cui and Z.B., this work has been filed as a US Provisional Patent Application, patent number 63/402,427. The other authors declare no competing interest.

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Nature Energy thanks George Chen, Min-Sik Park and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–50 and Tables 1 and 2.

Source data

Source Data Fig. 3

Rheology and XPS peak.

Source Data Fig. 4

Impedance and symmetric cell.

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Cycling data.

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Huang, Z., Lai, JC., Liao, SL. et al. A salt-philic, solvent-phobic interfacial coating design for lithium metal electrodes. Nat Energy 8, 577–585 (2023). https://doi.org/10.1038/s41560-023-01252-5

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