Supporting Information - Bottleneck of Diffusion and Inductive Effects in Li 10 Ge 1 x Sn x P 2 S 12

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1 Supporting Informtion - Bottleneck of Diffusion nd Inductive Effects in Li 10 Ge 1 x Sn x P 2 S 12 Thorben Kruskopf, Sen P. Culver,b, Wolfgng G. Zeier*,b Institute of Physicl Chemistry, Justus-Liebig-University Giessen, Heinrich-Buff- Ring 17, D Giessen, Germny. b Center for Mterils Reserch (LM), Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, D Giessen, Germny. S1

2 Figure S1: Log of pre-exponentil fctor σ 0 versus ctivtion energy E A for Li 10Ge 1 xsn xp 2S 12. The liner reltionship corresponds well with the Meyer-Neldel rule. S2

3 Figure S2: X-ry diffrction dt nd results of the Rietveld refinement of Li 10GeP 2S 12 (), Li 10Ge 2/3Sn 13P 2S 12 (b) nd Li 10SnP 2S 12 (c). Experimentl dt re shown s points, the red line denotes the clculted pttern nd the difference profile is shown in blue. Clculted positions of the Brgg reflections re shown s verticl ticks. S3

4 Figure S3: X-ry diffrction dt nd results of the Rietveld refinement of Li 10GeP 2S 12 (), Li 10Ge 2/3Sn 1/3P 2S 12 (b), Li 10Ge 1/3Sn 2/3P 2S 12 (c) nd Li 10SnP 2S 12 (d) using the full rnge (2Θ = ). Experimentl dt re shown s points, the red line denotes the clculted pttern nd the difference profile is shown in blue. Clculted positions of the Brgg reflections re shown s verticl ticks. Tble S1: Refined structurl prmeters for Li 10GeP 2S 12 t room temperture obtined from Rietveld refinement of XRD dt between Θ. tom Wyckoff tomic coordintes site x y z Occ. B iso / A " Li1 16h Li2 8g Li3 8f Li4 4c P1 4d (2) (6) Ge1 4d (2) (6) P2 2b (1) S1 8g (3) (2) (8) S2 8g (3) (2) (7) S3 8g (3) (2) (7) The spce group is P4 2/nmc (No. 137). Obtined lttice prmeters = (1) Å, c = (3) Å. Vlues in prentheses represent sttisticl errors on the lst significnt digit. Fit residuls (R p, R wp, R exp, S): 1.79, 2.25, 1.46, S4

5 Tble S2: Refined structurl prmeters for Li 10Ge 2/3Sn 1/3P 2S 12 t room temperture obtined from Rietveld refinement of XRD dt between Θ. tom Wyckoff tomic coordintes site x y z Occ. B iso / A " Li1 16h Li2 8g Li3 8f Li4 4c P1 4d (2) (8) Ge1 4d (2) 0.387(7) 2.96(8) Sn1 4d (2) 0.112(7) 2.96(8) P2 2b (1) S1 8g (2) (2) (7) S2 8g (2) (2) (7) S3 8g (2) (2) (6) The spce group is P4 2/nmc (No. 137). Obtined lttice prmeters = (9) Å, c = (2) Å. Vlues in prentheses represent sttisticl errors on the lst significnt digit. Fit residuls (R p, R wp, R exp, S): 1.43, 1.81, 1.38, Side phse: 0.79 ± 0.06 wt% Li 2SnS 3. 1 Tble S3: Refined structurl prmeters for Li 10Ge 1/3Sn 2/3P 2S 12 t room temperture obtined from Rietveld refinement of XRD dt between Θ. tom Wyckoff tomic coordintes site x y z Occ. B iso / A " Li1 16h Li2 8g Li3 8f Li4 4c P1 4d (2) (9) Ge1 4d (2) 0.292(9) 3.42(9) Sn1 4d (2) 0.208(9) 3.42(9) P2 2b (1) S1 8g (3) (3) (9) S2 8g (3) (2) (9) S3 8g (3) (2) (9) The spce group is P4 2/nmc (No. 137). Obtined lttice prmeters = (1) Å, c = (3) Å. Vlues in prentheses represent sttisticl errors on the lst significnt digit. Fit residuls (R p, R wp, R exp, S): 1.51, 1.94, 1.39, Side phse: 2.3 ± 0.5 wt% Li 2SnS 3. 1 S5

6 Tble S4: Refined structurl prmeters for Li 10SnP 2S 12 t room temperture obtined from Rietveld refinement of XRD dt between Θ. tom Wyckoff tomic coordintes site x y z Occ. B iso / A " Li1 16h Li2 8g Li3 8f Li4 4c P1 4d (2) (5) Sn1 4d (2) (5) P2 2b (1) S1 8g (3) (3) (9) S2 8g (3) (2) (8) S3 8g (3) (2) (8) The spce group is P4 2/nmc (No. 137). Obtined lttice prmeters = (1) Å, c = (3) Å. Vlues in prentheses represent sttisticl errors on the lst significnt digit. Fit residuls (R p, R wp, R exp, S): 1.39, 1.75, 1.27, Side phse: 2.8 ± 0.5 wt% Li 2SnS 3. 1 Tble S5: Reported lttice prmeter nd room temperture ionic conductivities for Li 10GeP 2S 12. literry source / A c / A V / A ³ c / σ RT / ms cm 1 This work (1) (3) Weber et l K, Neutron diffrction (6) (1) Hussoun et l K, X-ry: Cu-Kα 8.708(1) (6) Kym et l. 300 K, Neutron diffrction (2) (4) Kuhn et l K, Single crystl X-ry Sun et l K, X-ry: Cu-Kα Bron et l S6

7 Tble S6: Reported lttice prmeter nd room temperture ionic conductivities for Li 10SnP 2S 12. literry source / A c / A V / A ³ c / σ RT / ms cm 1 This work (1) (3) Bron et l (4) (9) K, Single crystl X-ry (300 K) Trhouchi et l K, X-ry: Cu-Kα 8.73(1) 12.76(2) Bron et l Tble S7: Fitted idelity fctor nd cpcitnces of the prllel combintion R/CPE. compound α C / pf C geom. / pf cm 2 Li 10GeP 2S (3) 24(2) 45(4) Li 10Ge 2/3Sn 1/3P 2S (3) 22(1) 42(3) Li 10Ge 1/3Sn 2/3P 2S (2) 20(2) 37(4) Li 10SnP 2S (3) 26(2) 49(4) Tble S8: Collected experimentl vlues for Li 10Ge 1 xsn xp 2S 12. compound c / σ RT / ms cm 1 σ 0 / K S cm 1 E A / ev ν D / s 1 Li 10GeP 2S (3) 9(1) 0.274(3) 4.15(4) Li 10Ge 2/3Sn 1/3P 2S (3) 8(1) 0.275(3) 4.00(4) Li 10Ge 1/3Sn 2/3P 2S (2) 9(1) 0.285(3) 3.89(4) Li 10SnP 2S (2) 15(2) 0.304(3) 3.73(3) S7

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