Reliability of Transport Properties for Bulk Thermoelectrics

Reliability of Transport Properties for Bulk Thermoelectrics Hsin Wang Oak Ridge National Laboratory Oak Ridge, TN USA

This project is supported by the International Energy Agency (IEA) under the Implementing Agreement on Advanced Materials for Transportation (AMT) 1

Managed by UT-Battelle for the Department of Energy

Most Cited Thermoelectric Papers 1.

Title: Thin-film thermoelectric devices with high room-temperature figures of merit Author(s): Venkatasubramanian, R; Siivola, E; Colpitts, T; et al. Source: NATURE Volume: 413 Issue: 6856 Pages: 597602 Published: OCT 11 2001 Times Cited: 1,558

2.

Title: Large thermoelectric power in NaCo2O4 single crystals Author(s): Terasaki, I; Sasago, Y; Uchinokura, K, Source: PHYSICAL REVIEW B Volume: 56 Issue: 20 Pages: 12685-12687 Published: NOV 15 1997 Times Cited: 1,217

3.

EFFECT OF QUANTUM-WELL STRUCTURES ON THE THERMOELECTRIC FIGURE OF MERIT Author(s): HICKS, LD; DRESSELHAUS, MS Source: PHYSICAL REVIEW B Volume: 47 Issue: 19 Pages: 12727-12731 Published: MAY 15 1993 Times Cited: 1,017

4.

Quantum dot superlattice thermoelectric materials and devices Author(s): Harman, TC; Taylor, PJ; Walsh, MP; et al. Source: SCIENCE Volume: 297 Issue: 5590 Pages: 2229-2232 Published: SEP 27 2002 Times Cited: 925

5.

Title: Enhanced thermoelectric performance of rough silicon nanowires Author(s): Hochbaum, Allon I.; Chen, Renkun; Delgado, Raul Diaz; et al. Source: NATURE Volume: 451 Issue: 7175 Pages: 163-U5 Published: JAN 10 2008 Times Cited: 909

6.

Title: Cubic AgPbmSbTe2+m: Bulk thermoelectric materials with high figure of merit Author(s): Hsu, KF; Loo, S; Guo, F; et al. Source: SCIENCE Volume: 303 Issue: 5659 Pages: 818-821 Published: FEB 6 2004Times Cited: 905

7.

Title: Filled skutterudite antimonides: A new class of thermoelectric materials Author(s): Sales, BC; Mandrus, D; Williams, RK Source: SCIENCE Volume: 272 Issue: 5266 Pages: 1325-1328 Published: MAY 31 1996 Times Cited: 833

8.

Title: High-thermoelectric performance of nanostructured bismuth antimony telluride bulk alloys Author(s): Poudel, Bed; Hao, Qing; Ma, Yi; et al. Source: SCIENCE Volume: 320 Issue: 5876 Pages: 634-638 Published: MAY 2 2008 Times Cited: 617

9.

Title: Skutterudites: A phonon-glass-electron crystal approach to advanced thermoelectric energy conversion applications Author(s): Nolas, GS; Morelli, DT; Tritt, TM Source: ANNUAL REVIEW OF MATERIALS SCIENCE Volume: 29 Pages: 89-116 Published: 1999Times Cited: 287

10. Title: Properties of single crystalline semiconducting CoSb3 Author(s): Caillat, T; Borshchevsky, A; Fleurial, JP Source: JOURNAL OF APPLIED PHYSICS Volume: 80 Issue: 8 Pages: 4442-4449 Published: OCT 15 1996Times Cited: 271 2


Mystery in Reporting Thermal Conductivity

ZT = s2σT/k k = αCpD

3


Ref. #6

• Thermal conductivity is not measured • Thermal conductivity is calculated

Annex VIII Participants • IEA-AMT Thermoelectric Annex – Annex lead: Oak Ridge National Laboratory (H. Wang) – USA: Clemson (T. Tritt, S. Zhu); Marlow (J. Sharp); Corning (A. Mayolet, J. Senawiratne) and ZT-Plus (F. Harris) – China: SICCAS (S.Q. Bai, L. Chen) – Canada: Natural Resource Canada (J. Lo); University of Waterloo (Holger Kleinke); University of Quebec at Chicoutimi (Laszlo Kiss) – Germany: Fraunhofer IPM (H. Böttner, J. König )

• IEA-AMT members countries: – – – – – 4

UK: NPL Finland: VTT Israel: Australia: Republic of Korea: KERI (H. W. Lee)


Marlow Materials Selected for Transport Properties Round-Robin Tests • Materials: Bi2Te3.005 (n-type) Bi0.5Sb1.5Te3 (p-type) • Four-sample Sets

– Thermal diffusivity: 12.7 mm diameter disk – Specific heat: 4 mm diameter disk – Seebeck coefficient and electrical resistivity: 2 x 2 x 15 mm3 bar, 3 x 3 x 12 m3 bar

• Temperature range: 300-500K • No ranking of the labs (lab numbers are assigned randomly in each plot)

5


Round-robin 1: Thermal Diffusivity

n-type p-type

Results from 8 labs 6


Round-robin 1: Seebeck Coefficient Lab #1 N 2x2

300

Lab #1 N 3x3 Lab #1 P 2x2 Lab #1 P 3x3 Lab #2 N 2x2 Lab #2 N 3x3 Lab #2 P 2x2

Seebeck Coefficient (µV/K)

200

Lab #2 P 3x3

p-type

Lab #3 N 2x2 Lab #3 N 3x3 Lab 33 P 2x2 Lab #3 P 3x3 Lab #4 N 2x2

100

Lab #4 N 3x3 Lab #4 P 2x2 Lab #4 P 3x3

2-point 0

Lab #5 N1 Lab #5 N2 Lab #5 P1

200

300

400

500

600

Lab #5 P2 Lab #6 N 2x2 Lab #6 N 3x3 Lab #6 P 2x2 Lab #6 P 3x3

-100

Lab #7 N 2x2 Lab #7 N 3x3

n-type

Lab #7 P 2x2 Lab #7 P 3x3 Marlow N Marlow P

-200

Lab #8 N 2x2 Lab #8 N 3x3 Lab #8 P 2x2

NIST SRM -300

7


Lab #8 P 3x3 Lab #9 N 2x2 Lab #9 N 3x3

Temperature (K)

Lab #9 P 2x2 Lab #9 P 3x3 NIST SRM

Round-robin 1: Electrical Resistivity Lab #1 N 2x2

4.00

Lab #1 N 3x3 Lab #1 P 2x2 Lab #1 P 3x3 Lab #2 N 2x2

Electrical Resisivity (mOhm-cm)

3.50


3.00


2.50

Lab #4 N 3x3

n-type

Lab #4 P 2x2

2-point

2.00

Lab #4 P 3x3 Lab #5 N1 Lab #5 N2 Lab #5 P1 Lab #5 P2 Lab #6 N 2x2

1.50

Lab #6 N 3x3 Lab #6 P 2x2

p-type

1.00

Lab #6 P 3x3 Lab #7 N 2x2 Lab #7 N 3x3 Lab #7 P 2x2 Lab #7 P 3x3 Marlow N

0.50

Marlow P Lab #8 N 2x2 Lab #8 N 3x3

0.00

Lab #8 P 2x2

250

350

450

Temperature (K)

8


550

Lab #8 P 3x3 Lan#9 N 2x2 Lab #9 N 3x3 Lab #9 P 2x2 Lab #9 3x3

Cp of Round-robin 1 with Debye Fit

p-type n-type

9


Round-robin #2 Started in October 2010 • Procedures for DSC prepared by ORNL • Two sets of p-type samples – Set #1: ORNL -> Clemson-> Corning -> ZT-Plus -> Germany -> China -> Canada – Set #2: China -> (Japan) -> Germany -> ORNL -> Clemson-> Corning -> ZT-Plus -> Canada

• Completed in September 2011 • Report to IEA-AMT: October 2011 • IEA-AMT Topical report November 2011 10 Managed by UT-Battelle for the Department of Energy

Round-robin 2: Seebeck Coefficient 350

Seebeck Coefficient (µV/K)

300 250 200 150 100 50 0 250

300

350

400

Temperature (K)

11 Managed by UT-Battelle for the Department of Energy

450

500

Lab #1 P1-1 Lab #1 P1-2 Lab #1 P2-1 Lab #1 P2-2 Lab #2 P1-1 Lab #2 P1-2 Lab #2 P2-1 Lab #2 P2-2 Lab #3 P1-1 Lab #3 P1-2 Lab #3 P2-1 Lab #3 P2-2 Lab #4 P1-1 Lab #4 P1-2 Lab #4 P2-1 Lab #4 P2-2 Lab #5 P1-1 Lab #5 P1-2 Lab #5 P2-1 Lab #5 P2-2 Lab #6 P1-1 Lab #6 P1-2 Lab #6 P2-1 Lab #6 P2-2 Lab #7 P1-1 Lab #7 P1-2 Lab #7 P2-1 Lab #7 P2-2 Marlow 2-point Contact

Round-robin 2: Electrical Resistivity 4

Resistivity (mOhm-cm)

3.5 3 2.5 2 1.5 1 0.5 0 250

300

350

400

Temperature (K)


450

500

Lab #1 P1-1 Lab #1 P1-2 Lab #1 P2-1 Lab #1 P2-2 Lab #2 P1-1 Lab #2 P1-2 Lab #2 P2-1 Lab #2 P2-2 Lab #3 P1-1 Lab #3 P1-2 Lab #3 P2-1 Lab #3 P2-2 Lab #4 P1-1 Lav #4 P1-2 Lab #4 P2-1 Lab #4 P1-2 Lab #5 P1-1 Lab #5 P1-2 Lab #5 P2-1 Lab #5 P2-2 Lab #6 P1-1 Lab #6 P1-2 Lab #6 P2-1 Lab #6 P2-2 Lab #7 P1-1 Lab #7 P1-2 Lab #7 P2-1 Lab #7 P2-2 Marlow 2-point Contact

Round-robin 2: Thermal Diffusivity


How Difficult is Thickness Measurement? α = 1.38d2/πt0.5

Thickness = 1.568 mm Thickness = 2.011 mm 14 Managed by UT-Battelle for the Department of Energy

Round-robin 2: Specific Heat


Cp of Round-robin 2 with Debye Fit


Calculation of ZT: P-type

Calculated from Full Scatter • PF: + 7.1 to 11.7% • K: +8.5 to 17.9% • ZT: + 11.7 to 20.9% 17 Managed by UT-Battelle for the Department of Energy

Summary • Reliability of transport property is critical for vehicle applications • IEA-AMT is addressing this issue timely • Round-robin #3: 300K-800K – GMZ half-heusler materials for the round-robin effort (March 2012) – Materials processed and machined at GMZ Energy and first set measurements completed in May 2012
