Supporting Information for. Fast Direct Synthesis and Compaction of Phase Pure. Thermoelectric ZnSb

Size: px

Start display at page:

Download "Supporting Information for. Fast Direct Synthesis and Compaction of Phase Pure. Thermoelectric ZnSb"

Hope Ross
5 years ago
Views:

Phase Pure Thermoelectric ZnSb Anders Bank Blichfeld, Bo Brummerstedt Iversen * Centre for Materials Crystallography,

1 Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C. This journal is The Royal Society of Chemistry 2015 Supporting Information for Fast Direct Synthesis and Compaction of Phase Pure Thermoelectric ZnSb Anders Bank Blichfeld, Bo Brummerstedt Iversen * Centre for Materials Crystallography, Department of Chemistry and inano, Aarhus University, Langelandsgade 140, DK-8000 Aarhus C, Denmark Figure S1: An overview of all PSM scans for the samples made for this study.

2 Figure S2: a) EDX map of the surface of a pellet made at 573 K, an applied pressure of 100 MPa, a ramping time of 10 minutes and reaction time of 5 minutes. b) Backscattered electron SEM picture of the same area as in a).

3 Figure S3: Synchrotron PXRD data on selected samples. The data was collected up to 2θ = 77, but a smaller range is shown here, to be able to distinguish the different peaks.

4 Figure S4: Two EDX line scans show that the composition of the SPS pressed ZnSb pellets with 2 at% extra Zn. The dashed lines in the graphs correspond to a composition of Zn:Sb = 4:3. The secondary electron SEM picture is a merge of two individual pictures. The uncertainties of the measurements are on the order of ± 5%.

5 Figure S5: XRD patterns (20 <2θ<70 Cu-K α ) on the top and bottom sides of pellets made at an applied pressure of 100 MPa, a ramping time of 10 minutes, a sintering time of 15 minutes, and a maximum temperature of 698 K. The current enters from the bottom. The migration of Zn-ions results in excess Zn at the top(right side in PSM scans), forming Zn 4 Sb 3.

6 Ramp (min) Hold time (min) Max temp.(k) Side top bottom top bottom top bottom top bottom top bottom # parametre # phases χ R Bragg (ZnSb) R Bragg Zn 4 Sb 3 ) R Bragg (Sb) R Bragg (Zn) wt % (ZnSb) 37.8(4) 94.6(8) 66.8(4) 95.6(7) 9.5(4) 94.8(6) 49.4(2) 94.4(7) 72.0(4) 96.7(6) wt %(Zn 4 Sb 3 ) 59.5(4) (2) (2) (3) (2) - wt %(Sb) 1.75(9) 5.4(2) 1.02(8) 4.43(7) (8) 2.19(5) 5.6(1) (7) wt %(Zn) 0.9(1) (8) (5) ZnSb Zn/Sb B iso 0.14(9) (4) (5) (4) - Zn-B iso (8) (5) (5) (5) - 0.2(3) Sb-B iso (6) - 1.5(8) - 1.1(7) (8) (6) a (2) (2) (1) (2) (2) (1) (2) (2) (1) (1) b (3) (2) (2) (2) (2) (2) (2) (2) (1) (2) c (3) (2) (2) (2) (2) (2) (3) (2) (1) (2) Zn 4 Sb 3 a (4) (3) (3) (4) (3) - c (4) (4) (3) (4) (3) - Sb a (5) (3) (6) (2) (2) (4) (2) (3) c (2) (1) (3) (9) (9) (2) (1) (2) Zn a (6) (9) (8) c 4.964(2) (3) (3) Tabel S1: Parameters from Rietveld analysis on data recorded on an in-house Rigaku Smartlab diffractometer. The data have been recorded on both sides of the pellets, to check for homogeneity.

7 Ramp (min) Hold time (min) Maximum temp. (K) Comments 2 at% (Sb) added # in the article iv i ii iii v # parametre # phases χ R Bragg (ZnSb) R Bragg (Sb) R Bragg (Zn 4 Sb 3 ) wt % (ZnSb) 95.8(3) 67.8(2) 94.7(2) 99.1(2) 96.4(2) wt % (Sb) 4.25(8) 8.47(6) 1.01(5) 0.89(5) 3.61(8) wt %(Zn 4 Sb 3 ) (2) 4.3(1) - - ZnSb Sb-x (6) (7) (5) (5) (6) Sb-y (5) (6) (4) (4) (5) Sb-z (5) (6) (4) (4) (5) Sb-B iso (2) (2) (2) (2) (2) Sb-occ B (1) (1) (8) (8) (9) B (7) (8) (6) (6) (7) B (6) (7) (5) (5) (6) B (1) (1) (9) (9) (1) B (1) (1) (8) (8) (9) B (9) (1) (8) (8) (8) Zn-x (1) (1) (9) (9) (1) Zn-y (9) (1) (7) (7) (8) Zn-z (1) (1) (9) (9) (1) Zn-B iso (5) (5) (4) (4) (4) Zn-occ. B (1) (2) 0.993(2) (2) 0.991(2) (2) 0.992(1) (2) 0.995(1) (2) B (2) (2) (1) (1) (2) B (1) (2) (1) (1) (1) B (2) (2) (1) (1) (1) B (1) (2) (1) (1) (1) B (1) (2) (1) (1) (1) a (Å) (3) (3) (2) (2) (3) b (Å) (4) (5) (3) (3) (4) c (Å) (4) (5) (3) (3) (4) Sb B iso 0.3(1) (4) 0.6(1) a (Å) (3) (9) (7) (4) (3) c (Å) (9) (3) (3) (2) (9) Zn 4 Sb 3 a (Å) (2) (6) - - c (Å) (2) (1) - - Tabel S2: Parameters from Rietveld analysis of five selected samples on synchrotron PXRD data recorded at 100 K.

8 Temperatur (K) # parametre # phases χ R Bragg (ZnSb) R Bragg (Sb) R Bragg (ZnO) R Bragg (ZnSb 2 O 4 ) wt % (ZnSb) 95.7(3) 95.5(3) 95.6(3) 95.6(3) 95.4(3) 95.5(3) wt % (Sb) 4.30(8) 4.46(8) 4.42(8) 4.36(8) 4.56(9) 4.50(9) wt % (ZnO) wt % (ZnSb 2 O 4 ) ZnSb Sb-x (6) (6) (6) (6) (6) (6) Sb-y (5) (5) (5) (5) (5) (5) Sb-z (5) (5) (5) (5) (5) (5) Sb-B iso 0.208(8) 0.268(9) 0.346(9) 0.420(9) 0.50(1) 0.56(1) Sb-occ Zn-x (1) (1) (1) (1) (1) (1) Zn-y (8) (8) (8) (8) (9) (9) Zn-z (1) (1) 0.87(1) 0.87(1) 0.87(1) 0.87(1) Zn-B iso 0.41(2) 0.50(2) 0.64(2) 0.76(2) 0.89(2) 0.98(2) Zn-occ (1) 0.988(1) 0.991(1) 0.991(1) 0.988(1) 0.987(1) a (Å) (3) (3) (3) (3) (3) (3) b (Å) (4) (4) (4) (4) (4) (4) c (Å) (4) (4) (4) (4) (4) (4) Sb z (4) (4) (4) (4) (4) (4) B iso 0.4(1) 0.4(1) 0.5(1) 0.6(1) 0.9(1) 0.9(1) a (Å) (3) (3) (3) (3) (3) (3) b (Å) (3) (3) (3) (3) (3) (3) c (Å) (9) (9) (9) (9) (9) (9) ZnO Zn/O B iso a (Å) b (Å) c (Å) ZnSb 2 O 4 a (Å) b (Å) c (Å) Tabel S3: Parameters from Rietveld analysis on multi-temperature synchrotron PXRD data measured on powder from the main body of the pellet synthesized at 100 MPa, a ramping time of 10 minutes, a sintering time of 15 minutes, and a maximum temperature of 698 K. The standard error of estimate is specified in parenthesis after a number. If no standard error of estimate is given, then the parameter has not been refined.

9 Temperatur (K) Low high 500 # parametre # phases χ R Bragg (ZnSb) R Bragg (Sb) R Bragg (ZnO) R Bragg (ZnSb 2 O 4 ) wt % (ZnSb) 95.7(3) 95.7(3) 95.7(3) 95.3(3) 86.2(5) wt % (Sb) 4.36(8) 4.28(8) 4.28(8) 4.31(8) 4.7(2) 7.47(9) wt % (ZnO) (5) wt % (ZnSb 2 O 4 ) ZnSb Sb-x (6) (6) (6) (6) Sb-y (5) (5) (5) (5) Sb-z (5) (5) (5) (5) Sb-B iso 0.63(1) 0.72(1) 0.79(1) 1.07(1) 1.55(1) 1.24(2) Sb-occ Zn-x (1) (1) (1) (1) Zn-y (8) (8) (9) (9) Zn-z (1) (1) (1) (1) Zn-B iso 1.09(2) 1.25(2) 1.39(2) 1.88(3) 2.47(3) 2.58(3) Zn-occ (1) 0.99(1) 0.991(1) 0.99(1) 1 1 a (Å) (3) (3) (3) (3) (5) (3) b (Å) (4) (4) (4) (4) (6) (4) c (Å) (4) (4) (4) (4) (6) (4) Sb z (4) (4) (4) (4) B iso 0.9(1) 0.9(1) 1(1) 1.277(1) 6.2(4) 1.68(9) a (Å) (3) (3) (3) (2) (2) (8) b (Å) (3) (3) (3) (2) (2) (8) c (Å) (8) (8) (9) (8) (8) (4) ZnO Zn/O B iso a (Å) (6) b (Å) (6) c (Å) (2) ZnSb 2 O 4 a (Å) b (Å) c (Å) Tabel S3 (continued): Parameters from Rietveld analysis on multi-temperature synchrotron PXRD data measured on powder from the main body of the pellet synthesized at 100 MPa, a ramping time of 10 minutes, a sintering time of 15 minutes, and a maximum temperature of 698 K. The standard error of estimate is specified in parenthesis after a number. If no standard error of estimate is given, then the parameter has not been refined.

10 Temperatur (K) After # parametre # phases χ R Bragg (ZnSb) R Bragg (Sb) R Bragg (ZnO) R Bragg (ZnSb 2 O 4 ) wt % (ZnSb) 51.5(4) 6.79(8) wt % (Sb) 17.9(1) 28.9(2) 59.6(2) 61.2(2) (4) wt % (ZnO) 19.6(6) 33.6(3) 34.8(2) 99.2(6) 31.8(4) wt % (ZnSb 2 O 4 ) (5) 0.83(7) 4.6(1) ZnSb Sb-x Sb-y Sb-z Sb-B iso 1.39(2) 1.56(3) 2.1(1) Sb-occ Zn-x Zn-y Zn-z Zn-B iso 3.10(4) 3.79(6) 5.0(2) Zn-occ a (Å) (4) (4) (1) b (Å) (5) (5) (1) c (Å) (5) (5) (1) Sb z (3) (6) B iso 1.42(4) 2.04(3) 2.51(1) 3.06(2) (2) a (Å) (5) (3) (2) (2) (4) b (Å) (5) (3) (2) (2) (4) c (Å) (2) (9) (7) (7) (1) ZnO Zn/O B iso 0 0.2(2) 0.53(4) 1.67(3) 1.73(2) 0.566(5) a (Å) (3) (2) (7) (6) (9) (9) b (Å) (3) (2) (7) (6) (9) (9) c (Å) (1) (7) (2) (1) (2) (2) ZnSb 2 O 4 a (Å) (2) (8) (3) b (Å) (2) (8) (3) c (Å) (3) (7) (3) Tabel S3 (continued): Parameters from Rietveld analysis on multi-temperature synchrotron PXRD data measured on powder from the main body of the pellet synthesized at 100 MPa, a ramping time of 10 minutes, a sintering time of 15 minutes, and a maximum temperature of 698 K. The standard error of estimate is specified in parenthesis after a number. If no standard error of estimate is given, then the parameter has not been refined.

Supporting information. Alkali Metal Ion Templated Transition Metal Formate. Framework Materials: Synthesis, Crystal Structures,

Supporting information. Alkali Metal Ion Templated Transition Metal Formate. Framework Materials: Synthesis, Crystal Structures, Supporting information Alkali Metal Ion Templated Transition Metal Formate Framework Materials: Synthesis, Crystal Structures, Ion Migration and Magnetism Espen Eikeland, 1 Nina Lock, 2 Mette Filsø, 1