Direct Energy Conversion: Chemistry,

Physics, Materials Science and

Thermoelectrics
Mercouri G Kanatzidis
MURI
KANATZIDIS
KANATZIDIS
MSU,CHEMISTRY
MSU, CHEMISTRY
TIM HOGAN HAROLD SCHOCK
SolidState
Solid StateChemistry
Chemistry
MSU, E. ENGINEERING MSU, Mechanical
Synthesis,Discovery
Synthesis, Discovery Measurements, Devices Engineering
Applications

ELDON CASE
MSU, Mechanical
S. D. MAHANTI CTIRAD
Engineering
CTIRAD UHER
UHER
Univ
Univ of
of Michigan
Metallurgy
MSU, PHYSICS Michigan
Physics
Physics
Theory Measurements
Measurements

American Physical Society Meeting, Baltimore March 2006

Heat to Electrical Energy Directly
Up to 20% conversion efficiency with right materials

Schock group
http://www.dts-generator.com/
 Thermoelectric applications
„ Waste heat recovery
• Automobiles
• Over the road trucks
• Utilities
• Chemical plants

„ Space power
„ Remote Power
Generation
„ Solar energy
„ Geothermal power
generation
„ Direct nuclear to electrical
 U.S. Energy Flow, 1999

web site: www.eia.doe.gov

Given that ~60% of energy becomes waste heat, even a 10% capture and conversion
to useful forms can have huge impact on overall energy utilization
 How does it work?
http://www.designinsite.dk

TE devices have no moving parts, no noise, reliable

Figure of Merit
0.25

δ = 0.0
δ = 0.1
0.2

electrical conductivity thermopower

0.15

σ⋅S
δ = 1.1
2
η

0.1 ZT = •T
κ total
0.05

Power factor
Total thermal conductivity
0
0 0.5 1 1.5

ZT
2 2.5 3 σ⋅S 2

avg

For Th = 800K
δ=Rc/R
Tc = 300K
 Today’s situation
„ The most efficient materials today
for power generation: PbTe and
TAGS (TeSbGeAg alloy)
„ The most efficient material for
cooling Bi2Te3 „Quantum Dot Layers in thin
„ PbTe: ZT~0.8 at 800 K (n-type) MBE-grown PbSe/PbTe
superlattices (Harman et al,
„ TAGS: ZT~1.2 700 K (p-type) ZT~3)
„ Bi2Te3-xSex: ZT~1 at 300 K
„ Further improvements are needed. PbTe
„ New materials needed PbSe 20 nm dot

Hicks LD, Dresselhaus MS Phys. Rev. B 47 1993 (24): 16631

Some promising systems under
investigation
„ half-Heusler alloys (ZrNiSn)
„ Zn4Sb3
„ Clathrates
„ Skutterudites (CoSb3)
„ Bulk nanocomposites based on PbTe
„ Bulk nanocomposites based on Si-Ge
„ AgSbTe2/PbTe, NaSbTe2/PbTe

See March 2006 issue of MRS Bulletin

 ZT and Electronic Structure
Isotropic structure
Anisotropic structure
mx m y
T τ
3/ 2

mz (r +1/ 2 ) For acoustic phonon scattering

Z max ∝γ e
κ latt
r=-1/2

m= effective mass E
τ=scattering time E
r= scattering parameter
κlatt= lattice thermal conductivity
T = temperature
γ= band degeneracy Ef

Large γ comes with

(a) high symmetry e.g.
rhombohedral, cubic k k k
(b) off-center band extrema Complex electronic structure
Selection criteria for candidate
materials
„ Narrow band-gap semiconductors
„ Heavy elements
ƒ High µ, low κ
„ Large unit cell, complex structure
ƒ low κ
„ Highly anisotropic or highly symmetric…
„ Complex compositions
ƒ low κ, complex electronic structure
Chemistry as a source of materials
Investigating the System:

A2Q + PbQ + M2Q3 –––––> (A2Q)n(PbQ)m(M2Q3)p

Map generates target compounds A=Ag, K, Rb, Cs
A2 Q M=Sb, Bi
Cubic materials
Q=Se, Te
ABmMQ2+m

Phases shown
are promising new TE
Materials
Rb0.5Bi1.83Te3

β-K2Bi8Se13
APb2Bi3Te7
A1+xPb4-2xBi7+xSe15 CsBi4Te6
PbQ
Pb6Bi2Se9 Pb5Bi6Se14 Pb5Bi12Se23
Bi2Q3
 Our first contact with cubic AgPbmSbTe2+m

„ AgBi3S5, KPbBi9Se13, KPb4Sb7Se15

„ CsPbBi3Te6, CsPb2Bi3Te7, CsPb3Bi3Te8,
„ RbPbBi3Te6, RbPb2Bi3Te7, RbPb3Bi3Te8,
„ KPbBiSe3, K2PbBi2Se5
„ K2Pb3Bi2Te7, KPb4SbTe6
AgPbmSbTe2+m (LAST-m)
AgPbm(Sb,Bi)Te2+m (BLAST-m)

Pb
Te
Sb
Ag

268
Unit cell volume (Å)

267

266

265

264 Vegard's law

263

6 8 10 12 14 16 18
m value
(1) (a) Rodot, H. Compt. Rend. 1959, 249, 1872-4.
(2) (a) Rosi, F. D.; Hockings, E. S.; Lindenblad, N. E. Adv. Energy Convers. 1961, 1, 151.
 (LAST-18) Ag1-xPb18SbTe20: Tunable properties
Changing x Comparison of ZT
Comparison of Thermopower 0.8
0 Ag0.73 (KF2207R2b)
Ag0.73 (KF2207R2b) 0.7 Ag0.76 (KF2228R3A2)
Ag0.76 (KF2228R3A2) Ag0.78 (KF2213R1B)
Ag0.78 (KF2213R1B) Ag0.80 (KF2213R2C)
-50 Ag0.80 (KF2213R2C) 0.6 Ag0.82 (KF2229R1A)
Thermopower (µ V/K)

Ag0.82 (KF2229R1A) Ag0.82 (KF2229R1B)

Ag0.82 (KF2229R1B) Ag0.82 (KF2229R1C)
Ag0.82 (KF2229R1C)
Ag0.82 (KF2229R1D)
0.5 Ag0.82 (KF2229R1D)
-100

ZT
0.4
-150
0.3

-200 0.2

0.1
-250
50 100 150 200 250 300 350 400 450 0
Temperature (K) 80 120 160 200 240 280 320 360 400
Comparison of Power Factors Temperature, K
50
Ag0.73 (KF2207R2b)
Ag0.76 (KF2228R3A2)
Ag0.78 (KF2213R1B)
40 Ag0.80 (KF2213R2C)
Power Factor S σ (µW/cm K )
2

Ag0.82 (KF2229R1A)
Ag0.82 (KF2229R1B)
Ag0.82 (KF2229R1C)
Ag0.82 (KF2229R1D)

30
2

20

10

0
50 100 150 200 250 300 350 400 450
Temperature (K)
 Synthesis: Heating cooling profiles
rock

950-1000 ºC Ingot properties very sensitive to cooling profile

T, K Cool to 50 ºC in
72 h Gravity induced inhomogeneity
13 deg/h
LAST-18

time, h
1000 ºC
T, K rock
Cool to 50 ºC
in 24 h

Wernick, J. H.. Metallurg. Soc. Conf. Proc. (1960), 5 69-87.

time, h
R. G. Maier Z. Metallkunde 1963, 311
Samples cooled slowly from
liquid to solid
„ Strongly varying
m= 8

S (µV/K)
composition from top to
bottom. m= 14
„ Strongly varying
properties from top to
bottom. m= 18

σ (S/cm)
„ “Sweet” spot exists with
very high ZT. m= 25
„ Mechanical properties
weak. m= 40

Strong composition grading along ingot

 Properties of Ag1-xPb18SbTe20
2.5

2000 -100 Lattice thermal conductivity

Lattice Thermal Conductivity (W/mK)

2 PbTe
-150
1500
-200
1.5
σ (S/cm)

S (µV/K)
1000 -250

1
-300
LAST-18
500
-350
0.5

0 -400
300 350 400 450 500 550 600 650 700 0.35 W/mK (Harman PbTe/PbSe superlattice)
0
Temperature, K 300 400 500 600 700 800

Temperature (K)
 Ag1-xPb18SbTe20
2.00
Ag Pb SbTe
0.86 18 20

1.50
ZT

1.00

0.50

0.00
300 350 400 450 500 550 600 650 700

Temperature, K

Hsu KF, Loo S, Guo F, Chen W, Dyck JS, Uher C, Hogan T, Polychroniadis EK, Kanatzidis MG Science, 2004, 303, 818
What is the origin of the TE
properties of AgPbmSbTem+2
systems?
 HRTEM
Coherently embedded nanocrystals
Pb- rich region

8-10 nm

Ag-Sb rich region

Polychroniadis, Frangis, 2004 LAST-18 κlatt=1.2 W/m-K at 300 K

PbTe κlatt=2.2 W/m-K at 300 K
Coherent compositional fluctuations in
AgPbmSbTem+2

FCC lattice

10 nm

Ag, Sb, Pb ordering

Driving force for segregation
Ag+/Sb3+ pair: stable

Ag Te Pb Te Pb Te Pb Pb Te Pb Te Pb Te Pb

Te Pb Te Pb Te Sb Te Te Pb Te Pb Te Pb Te

Pb Te Pb Te Pb Te Pb Pb Te Sb Te Pb Te Pb

Te Ag Te Pb Te Pb Te Te Ag Te Ag Te Pb Te

Pb Te Pb Te Sb Te Pb Pb Te Sb Te Pb Te Pb

Te Pb Te Pb Te Pb Te
Te Pb Te Pb Te Pb Te

Dissociated state..unstable Associated state..stable

Any +1/+3 pair

 LAST-m Solid solutions in (AgSbTe2)1-x(PbTe)x
0 20 40 60 80 100
20
Conductivity(mW/cm·K)

Klemmens-Drabble theory
(W/cmK)

18

16 m=65
Conductivity

14
m=62
m~62

12
Random alloy m~30
Thermal

10
Thermal

m=18
8 m=10 m=18
LatticeLattice

6
Experimental Points
below theoretical
4

0 20 40 60 80 100
AgSbTe2 PbTe
Mol % PbTe

T. Irie Jap. J. Appl. Phys. 1966, 5, 854

 P-type materials, LASTT 1000

„ (LASTT-m) Ag(Pb1-xSnx)mSbTe2+m 800

2 hours
rocking

Sn atoms act as acceptors

Temperature ( C)
„

o
600
„ Ag atoms act as acceptors
„ Sb atoms act as donors 400

„ e.g AgPb10Sn8SbTe20, 200

AgxPb7Sn3SbyTe12,
Very low lattice thermal conductivity
0
0 10 20 30 40 50 60
t (hours)
„ Good homogeneity

12000

Ag0.3Pb7Sn3Sb0.1Te12
10000
Intensity (arb. units)

8000

6000

4000

2000

20 30 40 50 60 70 80 90 100
2Theta
LASTT-16
Very low lattice thermal conductivity

κlatt =0.5 W/m·K at 650 K

Androulakis, Hsu, Hogan, Uher, Kanatzidis Advanced Mater. 2006, in press

LASTT-16: AgPb12Sn4Sb0.4Te20

320

280

240

Seebeck (uV/K)
200

160

120

80

40

0
320 400 480 560 640 720
T e m p e ra tu re , K

Androulakis, Hsu, Hogan, Uher, Kanatzidis Advanced Mater. 2006, in press

Figure of Merit LASTT (p-type)
2.0
Ag0.5 Pb6 Sn2 Sb0.2 Te10 (b)
1.8
Ag0.9 Pb5 Sn3 Sb0.7 Te10
1.6
Ag0.6 Pb7 Sn3 Sb0.2 Te12
1.4 LASTT
1.2
ZT

1.0 TAGS
0.8
0.6 PbTe
0.4
0.2
0.0
300 400 500 600 700 800

Temperature (K)

Androulakis, Hsu, Hogan, Uher, Kanatzidis Advanced Mater. 2006, in press

NaPb20SbTe22 (SALT-20)

Lattice Thermal conductivity (W/mK)

(B)
Pb Sn Te
1.5 0.9 0.1
not-nano

PbTe Se
1 0.9 0.1

(A)

0.5 Na Pb SbTe
1-x 20 22
nano

0
300 350 400 450 500 550 600 650 700
Temperature, K
50 nm
Poudeu, Hogan, Kanatzidis Angew. Chemie, 2006,
 SALT-20

Poudeu, Hogan, Kanatzidis Angew. Chemie, 2006,

State of the art - bulk
2.5

2
LAST
NaPb SbTe
20 22
1.5 LASTT
TAGS
ZT

Tl BiTe
9 6

1 Bi Te Ce Fe CoSb SiGe
CsBi Te 2 3 0.9 3 12
4 6

PbTe

0.5

0
0 200 400 600 800 1000 1200 1400

Temperature, K
Conclusions
„ New approaches are succeeding in raising ZT
„ The (A2Q)n(PbQ)m(Bi2Q3)p (Q=Se, Te) system is a
rich source of new materials
„ Several new promising compounds identified
ƒ strongly anisotropic
ƒ cubic
ƒ nanostructured
„ LAST, LASTT and SALT family of materials
ƒ nanostructured
ƒ superior ZT
„ Strong thermal conductivity reduction achieved
through nanostructuring
„ Doping studies and processing conditions are
important in ZT optimization
 Outlook
„ Further progress is expected on the TE figure of merit
„ Fundamental challenge:
• Translate current theoretical physical predictions on how to enhance
Power Factor (σ·S2) into actual chemistry in the laboratory
• Achieve minimum thermal conductivity (~0.3 W/mK) in a bulk
(nano)crystalline TE material
„ Research in new materials should focus on
• Understanding and controlling carrier scattering
• Controlling nanostructuring to manipulate phonon propagation
• Discovering new compounds
„ Long term: Waste heat recovery and conversion could be impacted
on a massive scale with low cost materials if ZT>2-3.
„ Thermoelectrics could help utilize existing depletable energy
resources more effectively
„ Thermoelectrics could also play role in renewable energy (e.g. solar,
etc)
Collaborators
„ Tim Hogan, Dept of Electrical
Engineering, MSU
„ S. D. (Bhanu) Mahanti, Dept. of
Physics, MSU
„ Ctirad Uher, Dept. of Physics, U of
Michigan
„ Simon Billinge, Physics, MSU
„ Eldon Case, MSU
„ Harold Schock, MSU
„ Bruce Cook, Iowa State
„ Terry Tritt, Clemson U
„ Art Schultz, Argonne NL
 TE Research group
„ Dr Duck young Chung
„ Joseph Sootsman
„ Dr Kuei fang Hsu
„ Dr Eric Quarez
„ Aurelie Guegen
„ Ferdinand Poudeu
„ Jun-Ho Kim
„ Dr John Androulakis