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Cryogenic X-ray photoelectron spectroscopy for battery interfaces

Nature volume 646, pages 850–855 (2025)Cite this article

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Abstract

Understanding the chemical environment of pristine interfaces is a long-sought goal in electrochemistry, materials science and surface science. A substantial understanding of one such interface, the solid electrolyte interphase (SEI) in lithium anodes, originates from X-ray photoelectron spectroscopy (XPS)1,2. However, room temperature (RT) combined with ultrahigh vacuum (UHV) can induce major SEI evolution from reactions and volatilization during XPS1,2. Thus, a technique is necessary for SEI stabilization. Here we develop cryogenic (cryo)-XPS with immediate plunge freezing and demonstrate SEI preservation. We discover substantially different SEI speciation and a thicker pristine SEI with cryo-XPS, free from RT-associated thickness reduction and alterations to important species, including LiF and Li2O, in UHV. This new access to pristine SEI composition enables performance correlations across diverse electrolyte chemistries. Primarily, we highlight the necessity of studying sensitive interfaces under cryogenic conditions.

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Fig. 1: Cryo-XPS transfer process for SEI preservation.
Fig. 2: Time-dependent SEI preservation and evolution.
Fig. 3: Reaction, UHV and X-ray beam effects on SEI chemical composition.
Fig. 4: Correlation between relative salt- and additive-derived SEI content and CE across diverse electrolyte chemistries.

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All data needed to evaluate the conclusions are present in the paper or the Supplementary Information. Source data are provided with this paper.

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Acknowledgements

S.B.S. acknowledges support from the TomKat Center Graduate Fellowship for Translational Research and the Link Foundation Energy Fellowship. G.D.A. acknowledges support from the Wallenberg Foundation Postdoctoral Scholarship Program. S.T.O. acknowledges support from the Schmidt Science Postdoctoral Fellowship. K.M.S.G. acknowledges support from NSF GRFP. Y.C. acknowledges the cryo-EM research support from the Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering under contract DE-AC02-76SF00515, and the support from Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies, of the US Department of Energy under the Battery Materials Research Program, the Battery500 Consortium program, and the CEI consortium program. S.F.B. acknowledges support from the Stanford StorageX initiative seed grant award. Part of this work was performed at the Stanford Nano Shared Facilities supported by the National Science Foundation under award no. ECCS-2026822. S.B.S. acknowledges the discussions with J. Lee and W. Zhang on cryo-XPS transfer. S.B.S. appreciates D. Li and J.H. Lee for providing the LHCE electrolyte.

Author information

Author notes

  1. Solomon T. Oyakhire

    Present address: Department of Materials Science and Engineering, University of California Berkeley, Berkeley, CA, USA

Authors and Affiliations

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

    Sanzeeda Baig Shuchi, Giulio D’Acunto, Solomon T. Oyakhire, Kenzie M. Sanroman Gutierrez & Stacey F. Bent

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

    Philaphon Sayavong

  3. Stanford Nano Shared Facilities, Stanford University, Stanford, CA, USA

    Juliet Risner-Jamtgaard

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

    Il Rok Choi & Yi Cui

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

    Yi Cui

  6. Department of Energy Science and Engineering, Stanford University, Stanford, CA, USA

    Yi Cui & Stacey F. Bent

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Contributions

S.B.S., S.F.B. and Y.C. conceived the idea and designed experiments. S.B.S. performed all the electrochemical experiments and conducted all the RT-XPS and cryo-XPS experiments. S.B.S. and G.D. developed the cryo-XPS transfer process. G.D. assisted with cryo-XPS experiments during the initial phase of the study. P.S. and S.T.O. assisted with experimental designs. K.M.S.G. assisted with data interpretation discussions and manuscript editing. J.R.-J. helped with cryo-XPS transfer development and instrument-related discussions. S.B.S. analysed and interpreted the data with assistance and feedback from all the authors. S.B.S. wrote the first draft of the manuscript, which was edited and revised by all the authors. I.R.C. assisted with electrochemical tests for CEI characterization. S.F.B. and Y.C. supervised the project in all aspects.

Corresponding authors

Correspondence to Yi Cui or Stacey F. Bent.

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Extended data figures and tables

Extended Data Fig. 1 Time-resolved high-resolution spectra for SEI with cryo-XPS.

a-f, All high-resolution spectra for (a) F 1 s, (b) Li 1 s, (c) N 1 s, (d) C 1 s, (e) O 1 s, (f) S 2p with cryo-XPS at 0 min and 60 min. The measurements are carried out in 1 M LiFSI/DME (1 M) electrolyte. Global normalization of all the peaks is performed with respect to the C-F/SOxFy peak in F 1 s high-resolution spectra in (a). The measurements are performed on one analysis spot to capture the SEI evolution decoupled from spatial heterogeneities in the SEI.

Extended Data Fig. 2 Time-resolved high-resolution spectra for SEI during cryo heated to RT-XPS.

a-f, All high-resolution spectra for (a) F 1 s, (b) Li 1 s, (c) N 1 s, (d) C 1 s, (e) O 1 s, (f) S 2p with cryo heated to RT-XPS at 0 min and 60 min. The measurements are carried out in 1 M LiFSI/DME (1 M) electrolyte. Global normalization of all the peaks is performed with respect to the C-F peak in F 1 s high-resolution spectra in (a). The measurements are performed on one analysis spot to capture the SEI evolution decoupled from spatial heterogeneities in the SEI. The analysis spot is the same as the one shown in Extended Data Fig. 1.

Extended Data Fig. 3 SEI preservation and evolution effects with cryo-XPS and RT-XPS on unwashed SEI.

a-b, High-resolution spectra for F 1 s peaks with (a) cryo-XPS and (b) cryo heated to RT-XPS at 0 min and at 60 min. c, Atomic concentration for unwashed SEI with cryo-XPS and cryo heated to RT-XPS at 0 min and at 60 min. The intensities of F 1 s spectra shown in (a) and (b) are normalized with respect to the SOxFy/ C-F peak. The measurements are performed on one analysis spot to capture the SEI evolution decoupled from spatial heterogeneities in the SEI. The measurements are carried out in 1 M LiFSI/DME (1 M) electrolyte.

Extended Data Fig. 4 Effect of gradual re-cooling on SEI preservation.

High-resolution F 1 s spectra for with cryo-XPS (blue, top), cryo-heated to RT-XPS (pink, middle), cryo-heated to RT, and then re-cooled to cryo-XPS (black, bottom), respectively. The measurements are performed on one analysis spot to capture the SEI evolution decoupled from spatial heterogeneities in the SEI. The measurements are carried out in 1 M LiPF6/EC-DEC (LP) electrolyte. An unwashed SEI sample is used as the composition is found to be more sensitive to temperature change in Extended Data Fig. 3.

Extended Data Fig. 5 Effect of cryo-XPS and RT-XPS on the SEI formed on Cu before Li plating.

High-resolution spectra for F 1 s peaks of SEI formed on Cu in 1 M LiPF6/EC-DEC (LP) electrolyte using a protocol of holding the Cu current collector at 10 mV above Li electrodeposition potential for 30 min using cryo-XPS and RT-XPS. This protocol ensures no Li is electrodeposited on Cu so that only electrolyte decomposition prior to Li plating can be studied.

Extended Data Fig. 6 Reaction effect on SEI chemical composition under cryo-XPS and RT-XPS conditions.

a-b, High-resolution spectra for (a) F 1 s peaks and (b) O 1 s peaks collected using cryo-XPS (blue, top), cryo heated to RT-XPS (pink, middle), and RT-XPS (yellow, bottom) with schematics showing SEI evolution. Global normalization across F 1 s and O 1 s is performed for the same electrolyte with respect to the C-F peak in F 1 s high-resolution spectra shown in (a). The measurements are carried out in 1 M LiPF6/EC-DEC (LP) electrolyte.

Extended Data Fig. 7 Cryo-XPS and RT-XPS comparison with cryo-(S)TEM EELS findings.

a, c, High-resolution spectra for (a) Li 1 s peaks and (c) C 1 s peaks with cryo-XPS and RT-XPS. b, Histogram showing thickness distribution of the SEI using cryo-TEM. d, C K-edge fine structure of Li dendrites using cryo-STEM EELS. e, Summary of key findings from cryo-XPS, cryo-STEM EELS and RT-XPS. The intensities of C 1 s and Li 1 s spectra shown in (a) and (c) are normalized to exhibit the same maximum intensity for both cryo-XPS and RT-XPS data. The measurements in (a)-(d) are carried out on (a), (c) 0.5 mAh cm–2 and (b), (d) 0.1 mAh cm–2 Li deposited on (a), (c) Cu foil and (b), (d) Cu-evaporated TEM grid at a current density of 1 mA cm–2 in 1 M LiPF6/EC-DEC (LP) electrolyte and rinsed by 60 µL DEC. tSEI refers to thickness of the SEI. The data shown in (b) and (d) are adapted with permission from Zhang, Z. et al., Science, DOI number: 10.1126/science.abi8703 [2022], AAAS15.

Extended Data Fig. 8 Temperature-dependent composition evolution effects on SEI species with cryo-XPS and RT-XPS in LHCE-SEI.

a-b, High-resolution spectra for (a) Li 1 s and (b) N 1 s peaks with cryo-XPS (blue, top), cryo heated to RT-XPS (pink, middle), and RT-XPS (yellow, bottom). Global normalization is performed with respect to the C-F peak in F 1 s high-resolution spectra shown in Fig. 3a. The measurements are carried out in LiFSI-1.2 DME-3 TTE by molar ratio (LHCE) electrolyte. We identify the peak near ~52 eV with cryo-XPS as Li3N (not Li0 metal) because it appears and disappears in conjunction with the same species peak in N 1 s region. Besides, Li is highly electropositive, so it is more favorable for Li to exist in its compound forms.

Extended Data Fig. 9 Effect of Ar+ ion sputtering on SEI composition during cryo-XPS and RT-XPS.

Average % atomic concentration change with sputtering for cryo-XPS and cryo heated to RT-XPS. The measurements are carried out in residual SEI from 4 M LiFSI/DME (4 M) electrolyte after 5 cycles. The error bars of XPS results are calculated from the analysis of three different spots of the same sample. Ar+ ion sputtering is destructive toward surface chemical composition1,2,58. So, the degree of composition change before and after Ar+ ion sputtering is used to understand the relative amount of stable species in the SEI.

Extended Data Fig. 10 Correlation between F/C ratio and CE in multiple electrolytes with cryo-XPS and RT-XPS.

a-b, CE (Supplementary Table 2) from Aurbach’s method15,46 in relation to the F/C ratio of SEI from (a) RT-XPS and (b) cryo-XPS. The measurements are carried out on 0.5 mAh cm–2 of Li deposited on Cu at a current density of 1 mA cm–2 in 1 M LiPF6/EC-DEC (LP), 90 vol% 1 M LiPF6/EC-DEC with 10 vol% FEC (LPF), 1 M LiFSI/DME (1 M), 4 M LiFSI/DME (4 M), and LiFSI-1.2 DME-3 TTE by molar ratio (LHCE) electrolytes. The error bars of XPS results are calculated from the analysis of three different spots of the same sample. Spearman rank correlation coefficient41 (ρ) is calculated from the average values of the CE and F/C ratio.

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Shuchi, S.B., D’Acunto, G., Sayavong, P. et al. Cryogenic X-ray photoelectron spectroscopy for battery interfaces. Nature 646, 850–855 (2025). https://doi.org/10.1038/s41586-025-09618-3

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