# Fileset

[Supplementary_material.pdf](https://mdr.nims.go.jp/filesets/bc0589be-ccc2-4bf9-9f66-2efaf19bcbc0/download)

## Creator

Antonio De Marco, Morteza Rahmanipour, Gioele Pagot, Giampaolo Lacarbonara

## Rights

[Creative Commons BY Attribution 4.0 International](https://creativecommons.org/licenses/by/4.0/)

## Other metadata

[Lithium interphase enhancement for applications in lithium-sulfur batteries](https://mdr.nims.go.jp/datasets/9f8d06ea-cf01-43e2-aebc-68ac24309c71)

## Fulltext

Microsoft Word - Supplementary_material.docxSupplementary material Lithium interphase enhancement for applications in lithium-sulfur batteries Antonio De Marcoaǂ, Morteza Rahmanipoura,#, Gioele Pagotb, Giampaolo Lacarbonaraaǂ* aDepartment of Chemistry “Giacomo Ciamician”, University of Bologna, via Piero Gobetti 85, 40129 Bologna, Italy  bSection of Chemistry for Technology, Department of Industrial Engineering, University of Padova, via F. Marzolo 9, I-35131 Padova, Italy *Corresponding Author: giampaol.lacarbonar2@unibo.it ǂ These authors contributed equally to this work # Present affiliation: PowerCo SE, Industriestrae Nord, 38239 Salzgitter, Germany      Imaging  Figure S1. Pictures of (a) pristine Li, (b) i. Li left 2.5 h in DOL: DME, ii. Li left 2.5 h DOL: DME with Ar bubbling, iii. T-Li.  Figure S2. EDS images of T-Li sample.   X-ray photoelectron spectroscopy  Figure S3. Survey XPS spectra and qualitative analysis of the surface elemental composition of the different samples.  Table S1. Surface elemental composition obtained from XPS studies. Sample C / at.% O / at.% Li / at.% F / at.% N / at.% S / at.% others / at.% Li 15.81 40.91 40.42 1.33 - - 1.53 Licyc 19.04 41.85 34.36 1.96 0.26 0.26 2.27 T-Li 13.65 39.05 45.83 0.86 - - 0.61 T-Licyc 46.06 28.62 20.58 2.15 0.42 0.14 2.03  Table S2. Surface carbon relative composition obtained from XPS studies. Sample C-H / at.% C-O/C-F / at.% CO32- / at.% Li 70.50 4.07 25.43 Licyc 65.37 13.94 20.69 T-Li 67.76 13.04 19.20 T-Licyc 71.72 12.45 15.83     Table S3. Surface oxygen relative composition obtained from XPS studies. Sample Li2O / at.% LiOH / at.% CO32- / at.% ads / at.% Li - 73.69 23.71 2.60 Licyc - 72.85 20.10 7.05 T-Li 12.29 65.24 21.19 1.28 T-Licyc - 52.53 39.30 8.16  Table S4. Surface lithium relative composition obtained from XPS studies. Sample LiOH/Li2O / at.% Li2CO3 / at.% Li 76.39 23.61 Licyc 81.22 18.78 T-Li 100.00 - T-Licyc 69.73 30.27  The 1H NMR spectrum recorded after dissolving the powder collected from the T-Li surface in DMSO-d6 is reported in Figure S4. The resulting spectrum reflects the soluble organic species formed on the lithium surface. A sharp singlet at ca. 8.5 ppm indicates the presence of aldehydic species, consistent with oxidative cleavage of the dioxolane ring. The intense, overlapping resonances between 3.1 and 3.7 ppm, partially covered by the residual water signal, are characteristic of protons α to oxygen atoms (–CH2–O–) and correspond to a mixture of DOL-derived fragments formed by polymerization. Minor features around 2.3–2.6 ppm suggest methylene groups adjacent to carbonyl functional groups (–CH2–CHO), while weaker aliphatic signals near 1.0–1.5 ppm can be attributed to trace dimethoxyethane (DME) or other low-molecular-weight by-products. Overall, the spectrum indicates that DOL underwent ring opening in the treatment conditions and subsequent oxidation, yielding a complex mixture of aldehydes, glycols, and ethers.  Figure S4. 1H NMR in DMSO-d6 of T-Li interphase obtained scratching the electrode after the treatment.   Symmetric cell performance   Figure S5. Voltage profiles in 1M LiTFSI DOL:DME with LiNO3 0.45 M of Li//Li symmetric cell at different current density (0.5 h stripping/0.5 h plating).            Figure S6. Impedance spectra and fitted curves for (a,b) T-Li//T-Li symmetric cells and (c) Li//Li  cells at fresh state and after 10, 25, 50, 75, 125, 225, 325, 425, 525 cycles at 30°C. The solid lines are the data fittings.        Figure S7. Evolution of QSEI, Rgb and Qgb over cycling for symmetric Li//Li and T-Li//T-Li cells. Table S5. Results from the fitting of the EIS recorded for the T-Li//T-Li cell at 30°C. Equivalent component Rel Ω RSEI  Ω QSEI (10-6) F ∙ sa-1 aSEI Rgb  Ω Qgb  (10-6) F ∙ sa-1 agb Rct Ω Qdl (10-2)  F ∙ sa-1 adl As assembled 4.1 555 9.2 0.859 200 4.65 0.870 117 0.18 0.696  ± 0.1 ± 3 ± 0.1 ±0.001 ±3 ±0.09 ± 0.002 ± 5 ± 0.02 ±0.002 10 cycles 4.5 169 9.6 0.879 43.8 7.5 0.899 44.9 0.60 0.624  ± 0.1 ± 3 ± 0.1 ± 0.001 ± 0.5 ± 0.2 ± 0.003 ± 0.9 ± 0.03 ± 0.001 25 cycles 4.5 120.9 8.69 0.883 23.6 8.7 0.915 44.9 1.07 0.578  ± 0.1 ± 0.4 ± 0.08 ± 0.001 ± 0.3 ± 0.2 ± 0.002 ± 0.9 ± 0.04 ± 0.001 50 cycles 5.0 27.7 7.83 0.905 4.67 3.6 1 46.6 2.53 0.539  ± 0.1 ± 0.1 ± 0.08 ± 0.001 ± 0.06 ± 0.2 ± 10-6 ± 0.6 ± 0.02 ± 0.002 75 cycles 5.2 17 8.7 0.92 4 3.3 1 35.2 2.75 0.514  ± 0.1 ± 1 ± 0.9 ± 0.02 ± 1 ± 0.9 ± 10-6 ± 0.8 ± 0.05 ± 0.006 125 cycles 6.32 4.9 2.39 1 7.8 7.7 1 25.9 4.77 0.447  ± 0.08 ± 0.2 ± 0.08 ± 10-6 ± 0.3 ± 0.5 ± 10-6 ± 0.7 ± 0.07 ± 0.007 225 cycles 8.78 31.0 15.8 0.814 3.4 2.16 1 37.8 2.97 0.534  ± 0.09 ± 0.4 ± 0.6 ± 0.007 ± 0.3 ± 0.09 ± 10-6 ± 0.6 ± 0.01 ± 0.006 325 cycles 11.67 62.2 16.4 0.763 4.1 1.41 1 50 1.92 0.52  ± 0.07 ± 0.4 ± 0.4 ± 0.003 ± 0.2 ± 0.04 ± 10-6 ± 2 ± 0.05 ± 0.01 425 cycles 12.9 76 14.5 0.791 21 37 0.65 71 1.12 0.519   ± 2 ± 0.2 ± 0.004 ± 2 ± 8 ± 0.02 ± 2 ± 0.01 ± 0.007 525 cycles 16.3 107 15.0 0.750 15 5 0.80 86 1.03 0.510   ± 2 ± 0.4 ± 0.002 ± 2 ± 2 ± 0.03 ± 4 ± 0.03 ± 0.008 Table S6. Results from the fitting of the EIS recorded for the Li//Li cell at 30°C. Equivalent component Rel Ω RSEI  Ω QSEI (10-6)  F ∙ sa-1 aSEI Rgb  Ω Qgb (10-6)  F ∙ sa-1 agb Rct Ω Qdl  (10-2) F ∙ sa-1 adl As assembled 9.22 127.7 2.109 0.866 11.6 1.22 1 22.8 0.138 0.479  ± 0.06 ± 0.2 ± 0.004 ± 0.001 ± 0.1 ± 0.02 ± 10-6 ± 0.2 ± 0.002 ± 0.002 10 cycles 18.5 31 3.9 0.993 111 1.53 0.861 21.3 0.188 0.495  ± 0.2 ± 4 ± 0.4 ± 0.006 ± 4 ± 0.08 ± 0.005 ± 0.4 ± 0.007 ± 0.002 25 cycles 25.3 77 2.5 0.914 77 2.0 0.860 26.7 2.2 0.491  ± 0.2 ± 4 ± 0.1 ± 0.005 ± 4 ± 0.2 ± 0.007 ± 0.7 ± 0.09 ± 0.003 50 cycles 19.7 175 1.57 0.863 10 1.9 0.990 30 3.11 0.618  ± 0.2 ± 2 ± 0.04 ± 0.004 ± 2 ± 0.4 ± 0.009 ± 3 ± 0.02 ± 0.002