Table 1 Thermodynamic stability, structural, and dispersion properties of ordered and disordered S/X site configurations in Li6PS5Cl, Li6PS5I, Li6.5Ge0.5P0.5S5I, and Li5.25PS4.25ClBr0.75

From: Non-local interactions determine local structure and lithium diffusion in solid electrolytes

System

ΔERE (meV/atom)

Volume (Å3)

Bulk modulus (GPa)

EDispersion (meV/atom)

% X at 4c site

Li6PS5Cl

Ordered S/Cl

0.0

964 (995, 1018, 877)

31.25

149 (493)

0

Disordered S/Cl

−5 (+50, +4, +5)

947 (956, 977, 866)

33.34

152 (499)

60%46,49

Li5.25PS4.25ClBr0.75

Ordered S/Cl

0.0

938 (950, 967, 887)

30.11

148 (440)

0

Disordered S/Cl

−5 (−9, −4, −3)

933 (944, 962, 880)

30.27

149 (443)

50%48

Li6PS5I

Ordered S/I

0.0

1006 (1018, 1066, 950)

33.45

162 (487)

0

Disordered S/I

+19 (+18, +20, +14)

999 (1014, 1063, 939)

33.81

163 (501)

<1%46

Li6.5Ge0.5P0.5S5I

Ordered S/I

0.0

1027 (1046, 1076, 958)

33.74

163 (524)

0

Disordered S/I

+12 (+12, +12, +4)

1022 (1040, 1069, 970)

33.84

164 (520)

3%47

  1. Comparative analysis of thermodynamic stability with (disordered) and without (ordered) S2−/X− site exchange (ΔERE) in Li6PS5Cl, Li6PS5I, Li6.5Ge0.5P0.5S5I, and Li5.25PS4.25ClBr0.75. Computed cell volumes, bulk modulus, and van der Waals stabilization (EDispersion) are detailed. Results obtained using the HSE06 method coupled with a many-body dispersion scheme are indicated. Corresponding values computed with PBEsol, optB88, and HSE06+TS approximations are tabulated within parentheses under the columns Volume and ΔERE. EDispersion computed with pairwise (TS) approximations are shown within the parenthesis.
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