Correlating Transport and Structural Properties in Li1+xAlxGe2 x(po4)3 (LAGP) Prepared from Aqueous Solution

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1 Supporting Information for Correlating Transport and Structural Properties in Li1+xAlxGe2 x(po4)3 (LAGP) Prepared from Aqueous Solution Manuel Weiss a, Dominik A. Weber a, Anatoliy Senyshyn b, Jürgen Janek a* and Wolfgang G. Zeier a* a Physikalisch-Chemisches Institut & Zentrum ür Materialforschung (ZfM/LaMa), Justus-Liebig-Universität Gießen, Heinrich-Buff-Ring 17, Gießen, Germany b Heinz Maier-Leibnitz Zentrum (MLZ), Technische Universität München, Lichtenbergstrasse 1, Garching, Germany *Corresponding authors: juergen.janek@phys.chemie.uni-giessen.de wolfgang.g.zeier@phys.chemie.uni-giessen.de S-1

2 Structural data for LAGP Representative refinements of laboratory X-ray diffraction data Figure S1: Laboratory X-ray diffraction data (open circles) and results of the Rietveld refinement (black line) for two different LAGP samples. The violet line depicts the profile difference. Vertical ticks mark the calculated Bragg positions of LAGP and some side phases: (a) Nominal composition Li 1.3Al 0.3Ge 1.7(PO 4) 3 (x = 0.3), sintered at 800 C Refined mass fractions: 98.6(7) % Li 1.28Al 0.28Ge 1.72(PO 4) 3, 1.43(4) % GeO 2; goodness of fit S = 1.60, R p = 4.11, R wp = 5.34, R exp = 3.34; (b) nominal composition Li 1.7Al 0.7Ge 1.3(PO 4) 3 (x = 0.7), sintered at 750 C Refined mass fractions: 69.2(6) % Li 1.48Al 0.48Ge 1.52(PO 4) 3, 6.36(6) % GeO 2, 0.8(1) % Li 4P 2O 7, 23.7(2) % Li 9Al 3P 8O 29; goodness of fit S = 1.68, R p = 4.23, R wp = 5.61, R exp = S-2

3 Synchrotron measurements The structural parameters for LAGP samples with different nominal compositions as obtained from refinements with space group R3 c of synchrotron data are listed in Tables S1 S16. The first table for each sample contains the atomic positions, isotropic atomic displacement parameters and occupancies. Atomic displacement parameters given as 0 Å 2 were refined anisotropically and are shown in the second table for each sample. Table S1: Structural parameters from the refinement of synchrotron data of a sample with nominal composition LiGe 2(PO 4) 3. Obtained lattice parameters: a = (0) Å, c = (1) Å. Refined mass fractions: % LAGP, 0.62 % GeO 2 (P4 2/mnm), 4.43 % GeO 2 (P3 121). Goodness of fit S = 1.87, R p = 6.43 %, R wp = 8.52 %, R exp = 4.56 %. P1 18e (5) O1 36f (10) (12) (3) O2 36f (9) (9) (3) Li1 6b Ge1 12c (0) Table S2: Anisotropic atomic displacement parameters from the refinement of synchrotron data of a sample with nominal composition LiGe 2(PO 4) 3. P (7) (8) (1) (4) (1) (3) O (2) 0.004(2) (2) (2) (5) (5) O (2) (2) (2) (13) (5) (5) Ge (3) (3) (0) (2) S-3

4 Table S3: Structural parameters from the refinement of synchrotron data of a sample with nominal composition Li 1.2Al 0.2Ge 1.8(PO 4) 3. Obtained lattice parameters: a = (2) Å, c = (6) Å. Refined mass fractions: 99.0(4) % LAGP, 1.03(2) % GeO 2. Goodness of fit S = 2.81, R p = 9.47 %, R wp = 12.5 %, R exp = 4.46 %. P1 18e (9) O1 36f (2) (2) (6) O2 36f (2) (2) (7) Li1 6b Ge1 12c (1) (0) Al1 12c (1) (0) Li2 36f (0) Table S4: Anisotropic atomic displacement parameters from the refinement of synchrotron data of a sample with nominal composition Li 1.2Al 0.2Ge 1.8(PO 4) 3. P (2) (2) (2) (8) (2) (5) O (4) (4) (4) (3) (9) (10) O (3) (3) (4) (3) (9) (10) Ge (6) (6) (1) (3) Al (6) (6) (1) (3) Table S5: Structural parameters from the refinement of synchrotron data of a sample with nominal composition Li 1.3Al 0.3Ge 1.7(PO 4) 3. Obtained lattice parameters: a = (1) Å, c = (5) Å. Refined mass fractions: 98.3(3) % LAGP, 1.73(2) % GeO 2. Goodness of fit S = 1.64, R p = 5.37 %, R wp = 7.05 %, R exp = 4.29 %. P1 18e (5) O1 36f (10) (12) (4) O2 36f (9) (9) (4) Li1 6b Ge1 12c (1) (0) Al1 12c (1) (0) Li2 36f (0) S-4

5 Table S6: Anisotropic atomic displacement parameters from the refinement of synchrotron data of a sample with nominal composition Li 1.3Al 0.3Ge 1.7(PO 4) 3. P (9) (10) (1) (5) (1) (3) O (2) (2) (3) (2) 0.001(6) (6) O (2) (2) (3) (2) (5) (6) Ge (4) (4) (1) (2) Al (4) (4) (1) (2) Table S7: Structural parameters from the refinement of synchrotron data of a sample with nominal composition Li 1.4Al 0.4Ge 1.6(PO 4) 3. Obtained lattice parameters: a = (1) Å, c = (4) Å. Refined mass fractions: 99.6(2) % LAGP, 0.31(1) % GeO 2, 0.11(1) % AlPO 4. Goodness of fit S = 1.73, R p = 4.96 %, R wp = 6.95 %, R exp = 4.01 %. P1 18e (4) O1 36f (9) (11) (3) O2 36f (8) (9) (3) Li1 6b (0) Ge1 12c (1) (0) Al1 12c (1) (0) Li2 36f (0) Table S8: Anisotropic atomic displacement parameters from the refinement of synchrotron data of a sample with nominal composition Li 1.4Al 0.4Ge 1.6(PO 4) 3. P (8) (9) (1) (4) (1) (2) O (2) (2) (2) (2) (5) (6) O (2) (2) (2) (2) (5) (5) Ge (4) (4) (0) (2) Al (4) (4) (0) (2) S-5

6 Table S9: Structural parameters from the refinement of synchrotron data of a sample with nominal composition Li 1.5Al 0.5Ge 1.5(PO 4) 3. Obtained lattice parameters: a = (1) Å, c = (4) Å. Refined mass fractions: 97.3(3) % LAGP, 2.67(2) % GeO 2. Goodness of fit S = 1.77, R p = 5.86 %, R wp = 8.07 %, R exp = 4.55 %. P1 18e (5) O1 36f (11) (14) (4) O2 36f (10) (11) (4) Li1 6b Ge1 12c (1) (0) Al1 12c (1) (0) Li2 36f (0) Table S10: Anisotropic atomic displacement parameters from the refinement of synchrotron data of a sample with nominal composition Li 1.5Al 0.5Ge 1.5(PO 4) 3. P (10) (10) (1) (5) (1) (3) O (3) (3) (3) (2) (6) (7) O (2) (2) (3) (18) (6) (7) Ge (5) (5) (1) (2) Al (5) (5) (1) (2) Table S11: Structural parameters from the refinement of synchrotron data of a sample with nominal composition Li 1.6Al 0.6Ge 1.4(PO 4) 3. Obtained lattice parameters: a = (1) Å, c = (3) Å. Refined mass fractions: 92.0(3) % LAGP, 5.37(6) % Li 9Al 3(P 2O 7) 3(PO 4) 2, 2.01(2) % GeO 2, 0.62(2) % AlPO 4. Goodness of fit S = 2.45, R p = 6.16 %, R wp = 8.72 %, R exp = 3.56 %. P1 18e (5) O1 36f (11) (14) (4) O2 36f (10) (11) (4) Li1 6b Ge1 12c (1) (0) Al1 12c (1) (0) Li2 36f (0) S-6

7 Table S12: Anisotropic atomic displacement parameters from the refinement of synchrotron data of a sample with nominal composition Li 1.6Al 0.6Ge 1.4(PO 4) 3. P (9) (10) (1) (5) (1) (3) O (3) 0.013(3) (3) (2) (6) (7) O (2) (2) (3) (2) (6) (7) Ge (5) (5) (1) (2) Al (5) (5) (1) (2) Table S13: Structural parameters from the refinement of synchrotron data of a sample with nominal composition Li 1.7Al 0.7Ge 1.3(PO 4) 3. Obtained lattice parameters: a = (1) Å, c = (4) Å. Refined mass fractions: 81.9(3) % LAGP, 12.83(8) % Li 9Al 3(P 2O 7) 3(PO 4) 2, 2.34(2) % GeO 2, 1.65(2) % AlPO 4 (C222 1), 1.27(3) % AlPO 4 (P112 1). Goodness of fit S = 2.02, R p = 6.14 %, R wp = 8.37 %, R exp = 4.14 %. P1 18e (5) O1 36f (12) (2) (5) O2 36f (11) (12) (5) Li1 6b Ge1 12c (1) (0) Al1 12c (1) (0) Li2 36f (0) Table S14: Anisotropic atomic displacement parameters from the refinement of synchrotron data of a sample with nominal composition Li 1.7Al 0.7Ge 1.3(PO 4) 3. P (10) (11) (1) (5) (2) (3) O (3) (3) (3) 0.007(2) (7) (8) O (2) (3) (3) (2) (7) (7) Ge (5) (5) (1) (3) Al (5) (5) (1) (3) S-7

8 Table S15: Structural parameters from the refinement of synchrotron data of a sample with nominal composition Li 1.8Al 0.8Ge 1.2(PO 4) 3. Obtained lattice parameters: a = (2) Å, c = (7) Å. Refined mass fractions: 68.0(4) % LAGP, 20.5(1) % Li 9Al 3(P 2O 7) 3(PO 4) 2, 5.84(3) % GeO 2, 5.63(6) % AlPO 4. Goodness of fit S = 2.64, R p = 9.83 %, R wp = 13.0 %, R exp = 4.95 %. P1 18e (11) O1 36f (2) (3) (9) O2 36f (2) (2) (9) Li1 6b Ge1 12c (2) (3) Al1 12c (2) (3) Li2 36f (1) Table S16: Anisotropic atomic displacement parameters from the refinement of synchrotron data of a sample with nominal composition Li 1.8Al 0.8Ge 1.2(PO 4) 3. P (2) (2) (3) (10) (3) (6) O (5) (6) (7) (5) (13) (2) O (4) (5) (6) (4) (13) (13) Ge (10) (10) (1) (5) Al (10) (10) (1) (5) Neutron measurements The structural parameters for LAGP samples with different nominal compositions as obtained from refinements with space group R3 c of neutron data are listed in Tables S17 S32. The first table for each sample contains the atomic positions, isotropic atomic displacement parameters and occupancies. Atomic displacement parameters given as 0 Å 2 were refined anisotropically and are shown in the second table for each sample. S-8

9 Table S17: Structural parameters from the refinement of neutron data of a sample with nominal composition LiGe 2(PO 4) 3. Obtained lattice parameters: a = (4) Å, c = (2) Å. Refined mass fractions: 95.1(3) % LAGP, 1.9(2) % GeO 2, 3.0(2) % Li 4P 2O 7. Goodness of fit S = 2.65, R p = 3.00 %, R wp = 3.56 %, R exp = 1.34 %. P1 18e (14) O1 36f (12) (12) (4) O2 36f (10) (10) (4) Li1 6b (14) 1.0 Ge1 12c (4) Table S18: Anisotropic atomic displacement parameters from the refinement of neutron data of a sample with nominal composition LiGe 2(PO 4) 3. P (5) (6) (5) (3) (2) (4) O (5) (5) (4) (4) (4) (3) O (4) (4) (4) (3) (4) (4) Ge (3) 0.019(3) (4) (13) Table S19: Structural parameters from the refinement of neutron data of a sample with nominal composition Li 1.2Al 0.2Ge 1.8(PO 4) 3. Obtained lattice parameters: a = (1) Å, c = (5) Å. Refined mass fractions: 96.8(4) % LAGP, 2.0(3) % GeO 2, 1.3(3) % Li 4P 2O 7. Goodness of fit S = 3.17, R p = 4.03 %, R wp = 5.16 %, R exp = 1.63 %. P1 18e (2) O1 36f (2) (2) (7) O2 36f (2) (2) (8) Li1 6b (3) 0.76(3) Ge1 12c (8) (10) Al1 12c (8) (10) Li2 36f 0.001(8) 0.270(7) 0.062(2) 0.5(3) 0.080(6) S-9

10 Table S20: Anisotropic atomic displacement parameters from the refinement of neutron data of a sample with nominal composition Li 1.2Al 0.2Ge 1.8(PO 4) 3. P (9) (12) 0.008(1) (6) (4) (8) O (1) (9) (9) (8) (7) (7) O (8) (9) (8) (7) (7) (7) Ge (8) (8) (8) (4) Al (8) (8) (8) (4) Table S21: Structural parameters from the refinement of neutron data of a sample with nominal composition Li 1.3Al 0.3Ge 1.7(PO 4) 3. Obtained lattice parameters: a = (8) Å, c = (4) Å. Refined mass fractions: 97.6(3) % LAGP, 2.4(3) % Li 4P 2O 7. Goodness of fit S = 3.13, R p = 3.80 %, R wp = 4.73 %, R exp = 1.47 %. P1 18e (2) O1 36f (2) (2) (6) O2 36f (2) (2) (7) Li1 6b (3) 0.73(3) Ge1 12c (7) (1) Al1 12c (7) (1) Li2 36f 0.004(7) 0.273(6) 0.062(2) 0.8(3) 0.084(5) Table S22: Anisotropic atomic displacement parameters from the refinement of neutron data of a sample with nominal composition Li 1.3Al 0.3Ge 1.7(PO 4) 3. P (7) (10) (9) (5) (4) (8) O (8) (8) (8) (7) (6) (6) O (7) (8) (7) (6) (6) (6) Ge (6) (6) (7) (3) Al (6) (6) (7) (3) S-10

11 Table S23: Structural parameters from the refinement of neutron data of a sample with nominal composition Li 1.4Al 0.4Ge 1.6(PO 4) 3. Obtained lattice parameters: a = (9) Å, c = (5) Å. Refined mass fractions: 98.5(3) % LAGP, 1.5(3) % Li 4P 2O 7. Goodness of fit S = 4.17, R p = 4.61 %, R wp = 5.95 %, R exp = 1.43 %. P1 18e (2) O1 36f (2) (2) (7) O2 36f (2) (2) (8) Li1 6b (3) 0.65(3) Ge1 12c (9) (1) Al1 12c (9) (1) Li2 36f 0.009(7) 0.232(5) 0.060(2) 1.6(3) 0.124(6) Table S24: Anisotropic atomic displacement parameters from the refinement of neutron data of a sample with nominal composition Li 1.4Al 0.4Ge 1.6(PO 4) 3. P (8) (12) 0.011(1) (6) (4) (8) O (9) (10) 0.019(9) (8) (7) (7) O (8) (10) (8) (7) (7) (7) Ge (8) (8) (9) (4) Al (8) (8) (9) (4) Table S25: Structural parameters from the refinement of neutron data of a sample with nominal composition Li 1.5Al 0.5Ge 1.5(PO 4) 3. Obtained lattice parameters: a = (9) Å, c = (4) Å. Refined mass fractions: 95.4(4) % LAGP, 1.3(3) % GeO 2, 3.2(3) % Li 4P 2O 7. Goodness of fit S = 3.68, R p = 4.37 %, R wp = 5.78 %, R exp = 1.57 %. P1 18e (2) O1 36f (2) (2) (8) O2 36f (2) (2) (8) Li1 6b (3) Ge1 12c (9) (1) Al1 12c (9) (1) Li2 36f 0.012(7) 0.227(5) 0.057(2) (6) S-11

12 Table S26: Anisotropic atomic displacement parameters from the refinement of neutron data of a sample with nominal composition Li 1.5Al 0.5Ge 1.5(PO 4) 3 P (8) (12) 0.012(1) (6) (4) (8) O (10) (10) (10) (8) (7) (8) O (9) (10) (8) (7) (7) (7) Ge (8) (8) (10) (4) Al (8) (8) (10) (4) Table S27: Structural parameters from the refinement of neutron data of a sample with nominal composition Li 1.6Al 0.6Ge 1.4(PO 4) 3. Obtained lattice parameters: a = (10) Å, c = (5) Å. Refined mass fractions: 86.6(6) % LAGP, 7.3(4) % Li 9Al 3(P 2O 7) 3(PO 4) 2, 2.5(3) % GeO 2, 3.6(3) % Li 4P 2O 7. Goodness of fit S = 4.36, R p = 4.75 %, R wp = 6.27 %, R exp = 1.44 %. P1 18e (2) O1 36f (2) (3) (9) O2 36f (2) (3) (9) Li1 6b (4) 0.50(3) Ge1 12c (11) (1) Al1 12c (11) (1) Li2 36f 0.014(6) 0.226(5) 0.058(2) 1.7(4) 0.163(7) Table S28: Anisotropic atomic displacement parameters from the refinement of neutron data of a sample with nominal composition Li 1.6Al 0.6Ge 1.4(PO 4) 3. P (10) (14) (12) (7) (5) (10) O (12) (12) (12) (10) (9) (9) O (10) (12) (10) (9) (9) (8) Ge (9) (9) (12) (4) Al (9) (9) (12) (4) S-12

13 Table S29: Structural parameters from the refinement of neutron data of a sample with nominal composition Li 1.7Al 0.7Ge 1.3(PO 4) 3. Obtained lattice parameters: a = (11) Å, c = (5) Å. Refined mass fractions: 80.1(5) % LAGP, 13.1(4) % Li 9Al 3(P 2O 7) 3(PO 4) 2, 3.5(3) % GeO 2, 3.2(3) % Li 4P 2O 7. Goodness of fit S = 3.87, R p = 4.58 %, R wp = 5.92 %, R exp = 1.53 %. P1 18e (3) O1 36f (3) (3) (9) O2 36f (3) (3) (9) Li1 6b (4) 0.48(3) Ge1 12c (12) (1) Al1 12c (12) (1) Li2 36f 0.016(6) 0.228(5) 0.057(2) 1.2(4) 0.165(7) Table S30: Anisotropic atomic displacement parameters from the refinement of neutron data of a sample with nominal composition Li 1.7Al 0.7Ge 1.3(PO 4) 3. P (10) (14) (14) (7) (5) (10) O (13) (13) (13) (11) (9) (9) O (11) (13) (11) (9) (9) (9) Ge (9) (9) (14) (5) Al (9) (9) (14) (5) Table S31: Structural parameters from the refinement of neutron data of a sample with nominal composition Li 1.8Al 0.8Ge 1.2(PO 4) 3. Obtained lattice parameters: a = (13) Å, c = (6) Å. Refined mass fractions: 72.0(6) % LAGP, 19.5(4) % Li 9Al 3(P 2O 7) 3(PO 4) 2, 4.8(3) % GeO 2, 3.7(4) % Li 4P 2O 7. Goodness of fit S = 3.72, R p = 4.78 %, R wp = 5.89 %, R exp = 1.58 %. P1 18e (3) O1 36f (3) (3) (11) O2 36f (3) (3) (11) Li1 6b (5) 0.45(4) Ge1 12c (14) (2) Al1 12c (14) (2) Li2 36f 0.014(7) 0.235(5) 0.058(2) 1.2(5) 0.166(8) S-13

14 Table S32: Anisotropic atomic displacement parameters from the refinement of neutron data of a sample with nominal composition Li 1.8Al 0.8Ge 1.2(PO 4) 3. P (12) 0.003(2) 0.014(2) (8) (6) (12) O (2) 0.035(2) 0.019(2) (13) (11) (11) O (14) (14) (13) (10) (11) (10) Ge (11) (11) 0.019(2) (5) Al (11) (11) 0.019(2) (5) Difference Fourier map of nuclear density Figure S2: (0 0 1) section of the difference Fourier map (F obs F calc) of nuclear density from the refinement of a sample with nominal composition Li 1.5Al 0.5Ge 1.5(PO 4) 3 against neutron diffraction data. During this refinement, only the Li(1) position (Wyckoff site 6b) was occupied. S-14

15 Evolution of pellet density Figure S3: Dependence of the relative density of the pellets used for electrochemical impedance measurements on the nominal lithium concentration. For calculation, the actual density was determined from the sample volume and weight, whereas the theoretical density was obtained from Rietveld refinements against laboratory X-ray diffraction data. S-15