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A free-standing lithium phosphorus oxynitride thin film electrolyte promotes uniformly dense lithium metal deposition with no external pressure

Nature Nanotechnology volume 18, pages 1448–1455 (2023)Cite this article

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Abstract

Lithium phosphorus oxynitride (LiPON) is an amorphous solid electrolyte that has been extensively studied over the last three decades. Despite the promise of pairing it with various electrode materials, LiPON’s rigidity and air sensitivity set limitations to understanding its intrinsic properties. Here we report a methodology to synthesize LiPON in a free-standing form that manifests remarkable flexibility and a Young’s modulus of ∼33 GPa. We use solid-state nuclear magnetic resonance and differential scanning calorimetry to quantitatively reveal the chemistry of the Li/LiPON interface and the presence of a well-defined LiPON glass-transition temperature of 207 °C. Combining interfacial stress and a gold seeding layer, our free-standing LiPON shows a uniformly dense deposition of lithium metal without the aid of external pressure. This free-standing LiPON film offers opportunities to study fundamental properties of LiPON for interface engineering for solid-state batteries.

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Fig. 1: Synthesis procedure and basic properties of FS-LiPON.
Fig. 2: Interfacial chemistry, thermal properties and mechanical properties of FS-LiPON.
Fig. 3: Electrochemical deposition and analysis on FS-LiPON.
Fig. 4: Stress analysis and proposed criteria for uniform lithium deposition.

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Data availability

Additional data related to this paper are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

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Acknowledgements

We gratefully acknowledge funding support from the US Department of Energy, Office of Basic Energy Sciences, under award number DE-SC0002357. The FIB/SEM in this work was performed in part at the San Diego Nanotechnology Infrastructure (SDNI) of the University of California San Diego, a member of the National Nanotechnology Coordinated Infrastructure, which is supported by the National Science Foundation (grant ECCS-2025752). NMR was performed under the auspices of the US Department of Energy by Lawrence Livermore National Laboratory under contract number DE-AC52-07NA27344. XPS and DSC were performed at the UC Irvine Materials Research Institute (IMRI) using instrumentation funded in part by the National Science Foundation Major Research Instrumentation Program under grant numbers CHE-1338173 and DMR-2011967.

Author information

Authors and Affiliations

  1. Materials Science and Engineering Program, University of California San Diego, La Jolla, CA, USA

    Diyi Cheng, Thomas Wynn, Yangyuchen Yang & Ying Shirley Meng

  2. Department of NanoEngineering, University of California San Diego, La Jolla, CA, USA

    Bingyu Lu, Bing Han, Ryosuke Shimizu, Bhagath Sreenarayanan, Han Nguyen, Weikang Li, Guomin Zhu, Minghao Zhang & Ying Shirley Meng

  3. Physical and Life Science Directorate, Lawrence Livermore National Laboratory, Livermore, CA, USA

    Maxwell Marple

  4. Nuclear Engineering Department, University of California Berkeley, Berkeley, CA, USA

    Jeffery Bickel & Peter Hosemann

  5. Pritzker School of Molecular Engineering, University of Chicago, Chicago, IL, USA

    Ying Shirley Meng

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  1. Diyi Cheng
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Contributions

D.C., M.Z. and Y.S.M. conceived the ideas. D.C., T.W., B.L., R.S. and B.S. prepared the thin-film samples. The FS-LiPON Li–Cu cell was designed by D.C. B.H., M.Z. and G.Z., and fabricated by D.C. M.M. performed and analysed ss-NMR measurements. D.C. conducted cryo-FIB/SEM and electrical measurements. D.C. and H.N. collected X-ray diffraction data. D.C., J.B. and P.H. collected and analysed the nanoindentation data. D.C., Y.Y. and W.L. collected XPS data. D.C., M.Z., Y.S.M., T.W., M.M., G.Z. and B.H. co-wrote the paper. All authors discussed the results and commented on the paper. All authors have approved the final paper.

Corresponding authors

Correspondence to Minghao Zhang or Ying Shirley Meng.

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The authors declare no competing interests.

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Extended data

Extended Data Fig. 1 Optical appearance of FS-LiPON film.

a, Photo of a piece of transparent and flexible FS-LiPON film. b, FS-LiPON films with different sizes in a glass vial.

Extended Data Fig. 2

Cross-section image of FS-LiPON with EDS mapping overlaid on the left part.

Extended Data Fig. 3 XRD measurement and surface EDS mapping on FS-LiPON film.

a, XRD pattern of FS-LiPON thin film. b, SEM image and EDS mapping on the surface of FS-LiPON.

Source data

Extended Data Fig. 4 XPS spectra of O 1s, N 1s, P 2p and Li 1s regions collected on FS-LiPON and sub-LiPON thin film.

Note that the peak located at 403.5 eV in N 1s region of sub-LiPON can be attributed to NO2− species, which is not present in the FS-LiPON.

Source data

Extended Data Fig. 5

XPS survey spectra of FS-LiPON and sub-LiPON films.

Source data

Extended Data Fig. 6 EIS testing for FS-LiPON film.

a, Testing configuration for the EIS measurement. b, EIS result collected on sub-LiPON.

Source data

Extended Data Fig. 7 Li7 MAS NMR spectrum of Li/FS-LiPON sample.

The spectrum clearly shows the presence of Li metal in Li/FS-LiPON sample.

Source data

Extended Data Fig. 8 Air exposure test on FS-LiPON film.

Photos of the same piece of FS-LiPON film before air exposure (a) and after air exposure (b), showing the film shape change due to stiffening.

Extended Data Fig. 9 Flexibility test on FS-LiPON film.

Time-lapse series of images during the flexibility test on FS-LiPON films with thicknesses of 1.7 μm, 2.6 μm and 3.7 μm, respectively. A flathead tweezer was used to apply force on the FS-LiPON films whilst a video was taken to record the bending and breakage of the film. As the time-lapse series of images show, all the FS-LiPON films exhibit remarkable flexibility upon bending. Right before film breakage, the 1.7-mm-thick film shows a high extent of bending compared with the 3.7-mm-thick film, indicating a higher flexibility.

Extended Data Table 1 Existing methods for LiPON synthesis
Full size table

Supplementary information

Supplementary Information

Supplementary Figs. 1–12 and Discussion.

Supplementary Video 1

A live demonstration of the flexibility and transparency of the FS-LiPON film.

Supplementary Video 2

A live demonstration of the stiffening of the FS-LiPON film after air exposure.

Supplementary Video 3

A live demonstration of the bending test of the FS-LiPON film.

Source data

Source Data Fig. 1

Source data of the XPS plot, EIS and DC polarization result in Fig. 1.

Source Data Fig. 2

Source data of the ss-NMR results, DSC measurement and nanoindentation results in Fig. 2.

Source Data Fig. 3

Source data of the Li plating voltage curve in Fig. 3.

Source Data Fig. 4

Source data of the interfacial stress analysis in Fig. 4.

Source Data Extended Data Fig. 3

Source data of the XRD results in Extended Data Fig. 3.

Source Data Extended Data Fig. 4

Source data of the detailed XPS spectra in Extended Data Fig. 4.

Source Data Extended Data Fig. 5

Source data of the survey XPS spectra in Extended Data Fig. 5.

Source Data Extended Data Fig. 6

Source data of the EIS plot in Extended Data Fig. 6.

Source Data Extended Data Fig. 7

Source data of the 7Li NMR spectrum in Extended Data Fig. 7.

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Cheng, D., Wynn, T., Lu, B. et al. A free-standing lithium phosphorus oxynitride thin film electrolyte promotes uniformly dense lithium metal deposition with no external pressure. Nat. Nanotechnol. 18, 1448–1455 (2023). https://doi.org/10.1038/s41565-023-01478-0

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