| PXRD (Panalytical Empyrean diffractometer; Cu Kα fine-focus sealed tube; PIXcel3D detector; λ = 1.5406 Å; 2θ = 10–90°; 0.02° per step) | Only a big hump was observed; generally, a hump in the low-angle region indicates the presence of an amorphous state |
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| ³¹P MAS NMR deconvolution (Varian 850 MHz spectrometer; 1.6 mm T3 probe and zirconia rotor; 20 kHz MAS; 103.5 kHz RF field; 2.45 µs 90° pulse; 64 scans; 150 s recycle delay; 85 % H₃PO₄ = 0 ppm; ssNake) | Li₃PS₄ glass: 83.9 ppm; PS₄³⁻ units accounted for 95.6 at %; Li₄P₂S₆ glass: 108.1 ppm, ratio 4.4 % |
Hongtao Qu. “Overlooked impacts of ball milling on the structure of Li₃PS₄-Li₂S cathode composite.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007625/v1
A separate supporting information file was not found among the files available from the ChemRxiv record
| PXRD (Panalytical Empyrean diffractometer; Cu Kα fine-focus sealed tube; PIXcel3D detector; λ = 1.5406 Å; 2θ = 10–90°; 0.02° per step) | Clear diffraction peaks due to Li₂S crystals; the same gLPS background profile was observed underneath the Li₂S diffraction peaks |
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| ³¹P MAS NMR deconvolution (Varian 850 MHz spectrometer; 1.6 mm T3 probe and zirconia rotor; 20 kHz MAS; 103.5 kHz RF field; 2.45 µs 90° pulse; 64 scans; 150 s recycle delay; 85 % H₃PO₄ = 0 ppm; ssNake) | No obvious changes were observed compared with gLPS; Li₃PS₄ glass: 84.0 ppm; PS₄³⁻ units accounted for 95.0 at %; Li₄P₂S₆ glass: 108.5 ppm, ratio 5.0 % |
| 2D ⁷Li-⁷Li MAS EXSY (Varian 400 MHz spectrometer; 4 mm Chemagnetics probe and zirconia rotor; 10 kHz MAS; standard three 90° pulse sequence; 16 scans; 10 s recycle delay; tₘᵢₓ = 1, 10, 100 ms; LiCl solution = 0 ppm; ssNake) | Compared with cLPS-Li₂S, the difference was non-discernible |
| ⁶Li MAS NMR (Varian 400 MHz spectrometer; 4 mm Chemagnetics probe and zirconia rotor; 10 kHz MAS; 5 µs 90° pulse; 64 scans; 1000 s recycle delay; LiCl solution = 0 ppm; ssNake) | The left peak was assigned to Li₂S and the right peak to Li in LPS; the spectra were not quantitative and could not provide more detailed information because the ⁶Li relaxation in Li₂S was incomplete even after 40000 s |
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| ³¹P MAS NMR (Varian 850 MHz spectrometer; 1.6 mm T3 probe and zirconia rotor; 20 kHz MAS; 103.5 kHz RF field; 2.45 µs 90° pulse; 64 scans; 150 s recycle delay; 85 % H₃PO₄ = 0 ppm; ssNake) | Sharp line at 87 ppm, attributed to PS₄³⁻ tetrahedra in LPS crystals |
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| PXRD (Panalytical Empyrean diffractometer; Cu Kα fine-focus sealed tube; PIXcel3D detector; λ = 1.5406 Å; 2θ = 10–90°; 0.02° per step) | All diffraction peaks were identified as belonging to either cubic Li₂S or orthorhombic β-Li₃PS₄; only a few characteristic β-Li₃PS₄ diffraction peaks appeared |
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| ³¹P MAS NMR deconvolution (Varian 850 MHz spectrometer; 1.6 mm T3 probe and zirconia rotor; 20 kHz MAS; 103.5 kHz RF field; 2.45 µs 90° pulse; 64 scans; 150 s recycle delay; 85 % H₃PO₄ = 0 ppm; ssNake) | Several broad peaks were observed; a fraction of LPS glasses formed after high-energy ball milling; Li₃PS₄ glass: 83.4 ppm, 53.4 %; Li₃PS₄ crystal: 87.2 ppm, 33.1 %; Li₄P₂S₆ glass: 108.4 ppm, 5.7 %; Li₄P₂S₇ glass: 89.7 ppm, 7.8 % |
| 2D ⁷Li-⁷Li MAS EXSY (Varian 400 MHz spectrometer; 4 mm Chemagnetics probe and zirconia rotor; 10 kHz MAS; standard three 90° pulse sequence; 16 scans; 10 s recycle delay; tₘᵢₓ = 1, 10, 100 ms; LiCl solution = 0 ppm; ssNake) | Diagonal contour peaks indicated Li ions residing in cLPS and Li₂S; Li ion exchange occurred at tₘᵢₓ = 1 ms as small cross peaks emerged; at 100 ms, pronounced cross peaks were observed, indicating that large amounts of Li ions were involved in the exchange process |