Nanocomposites and Nanothermoelectrics

Wenqing Zhang( 张文清 ), Lidong Chen( 陈立东 )

Shanghai Institute of Ceramics,
Chinese Academy of Sciences
Shanghai, China

Oct 17, 2009

1
 Basic principle of thermoelectrics (TE)
Carnot efficiency
Th  Tc 1  ZT  1
max  
Th 1  ZT  Th Tc

Th V S= V / T
ZT
TC TH
Tc

Seebeck effect was discovered in 1821

 热电现象的物理基础
Thermoelectrics and Conjugated Physical Properties
Thermoelectric phenomena of p-type semiconductor

diffusion of hole ZT SL+ e)

S 
S 
TT00 TT 0+T
0+T
S2/

low temperature high temperature

region region
(a) Initial stage
n
V 
n ~ 10 19 cm -3

＋ － ee= LT
TT00 T0T+T
0+T

high temperature
LL
low temperature
region region n

(b) Under equilibrium S= V / T Insulators Semiconductors Metals

Bulk Mater. ZT ~ 1.0 (1960-1995); Narrow-gap Semiconductor

~ 1.0-1.3 (1995- ) 窄带半导体 Eg~(5-10)kBT.
 Timeline of ZT

3.0
New comp: PGEC, etc
Composite: Nano-particle dispersion Low dimension
2.5 PbSeTe/PbTe QD (MIT)
ZT > 1.0
FIGURE OF MERIT (ZT) max

Bi2Te3/Sb2Te3 SL (RTI)
2.0
Multiple filled CoSb3
Narrow Eg:
1.5 Bi2Te3 CoSb3: Ce, Ba, Yb, Sm
PbTe ZT<1.0
CoSb3: Ce+Ba, Ce+Ca
Si0.8Ge0.2
1.0 CoSb3/C60, ZrNiSn/ZrO2
Bi2Te3 PbTe Bi2Te3-based composite
CsBiTe
0.5 Si0.8Ge0.2 YbMnSb Clathrate

0.0
1940 1960 1980 2000 2020
YEAR
 Phonon Glass and Electron Crystal
 Crystal with intrinsic lattice
voids;
 Impurity partially filling in
the voids.
ZT = S2T/(kL+ ke)
 EC/Electron Crystal:
Crystal-like electron
transport
 PG/Phonon Glass:
Glass-like phonon(thermal)
transport
 Only realized in compounds
with very special crystal
structure – caged.
 Other systems?
 Multiple-filled Skutterudites
–Phonon Glass Electron Crystal Materials with high ZTs

1.8 • Ba0.08La0.05Yb0.04Co4Sb12.05
Triple-filled
1.6  Ba0.10La0.05Yb0.07Co4Sb12.16

1.4
ZTave = 1.2
Ba0.08Yb0.09Co4Sb12
1.2
Ba0.24Co4Sb12
1.0 Bi2Te3 Yb0.12Co4Sb12
ZT

0.8
PbTe SiGe
0.6
0.4
0.2
0.0 7.8Å
200 400 600 800 1000 1200 1400
T (K)
Chen LD, Zhang W, Yang J et al.
PRL(2005), PRB(2006,2007),APL(2007,2008,2009), to be submitted (2009)
US patents (2007,2008,2009)
 State-of-the-art high ZT materials

System Max ZT Approach Reason

CoSb3-based ~1.7 bulk kL reduction
~ 1.45 nanocomposite
Bi2Te3-based ~ 1.5 thin film
nanocomposite kL reduction
PbTe-based(LAST) ~ 1.5 nanocomposite kL reduction
~ 1.5 bulk Enhanced PF
GeTe-based(TAGS) ~ 1.6 nanocomposite kL reduction
Si-Ge-based ~ 1.3 nanocomposite kL reduction
Si-nanowire ~ 0.8* nanowire ???
kL: Lattice thermal conductivity
PF: power factor (=S2
Role of Lower Dimensions in Thermoelectrics
Density of States (DOS) for Low D

 2 T
ZT  Large variation of DOS yields large
( E   L ) Seebeck Coefficient;
DOS
S Low dimension yields large dn(E)/dE
E EF

ZT ≈ S2≈ S2n
 kT 2 2
  ln  
S B
 E  ZT2D ≥ ZT3D
3e EF
限域效应和界面效应及其协同作用
Collective Effects in Nanocomposites: Size and Interfaces

块状低维复合材料系统
Thermoelectric Nanocomposites

phonons

particles

PGEC:
电子 (electron)
声子 (phonon)
 电热输运规律与调控机制
Compounds, Size Effects and Interface Effects

 Nano
 Bulk Nanocomposites
 Bulk Nanocomposite

SPS ： Non-
equilibrium
Bulk nanocomposite ：
 In situ nanoparticle formation plus SPS
 melt-spinning(MS) plus SPS
 Chemical synthesis plus SPS
 Mechanical alloy(MA) plus SPS
11
 In-situ preparation of YbyCo4Sb12/Yb2O3 nano-composites

Precipitation

CoSb3 ＋ Yb Yby+xCo4Sb12 YbyCo4Sb12 ＋ xYb

y+x
Oxidation
Grain-
晶界处
boundary
纳米颗粒

Using stable SPS

Yb2O3
partial filler Inside
晶粒内
Grain
to realize 纳米颗粒
nanocomposite YbyCo4Sb12

Selective oxidation of Yb leads to the formation of

homogeneously dispersed nano-size oxide particles.
 severed as effective phonon scattering centers.

Chen, Zhang, Appl. Phys. Lett. (2006); J. Appl. Phys. (2005, 2007); China patent 12
 TE performance of YbyCo4Sb12/Yb2O3

ZT=ST/
ZT=S 22
1.5 T/
Nolas
Sales
1.0 Anno

ZT
0.5 y =0.15
y =0.21/Yb2O3
y =0.25/Yb2O3
0
300 400 500 600 700 800 900
Temperature (K)
L was greatly depressed by the Yb2O3 nano particles dispersed inside
L was greatly depressed by the Yb2O3 nano particles dispersed inside
grain
grainand
andon
onthe
thegrain-boundary.
grain-boundary.ZT
ZT～～ 1.3
1.3

Appl. Phys. Lett. (2007, 2006, 2003); China Patent 13

In-situ formed YbyCo4Sb12/GaSb nano-composites

 GaSb: 5-10 nm
 Grain boundary
& inside grain
 S also improved
 ZT > 1.4

Xiong, Chen, Zhang, SICCAS(2009)

 Composite
Design ofThermoelectric Materials
Nanothermoelectrics
Electron Atoms Cluster Grain Macro

Size effect Interface effect

Key Structural Unit
DOS

3D

Energy (meV)

 Thermoelectric transport at electronic and atomic levels ；

 Size effects from nano dispersions ；
 Interface structure and Interface-induced effects ；
 Correlation between local properties and global performance.

Structure-property relationship study: expt + theory

 Performance prediction for Thermoelectrics

1. Electronic structure issue: band gap problem. ZT = S2T/k

2. Electrical transport: Power Factor = S2
A. near equilibrium distribution (Boltzmann transport equation)

  e  (
2 f 0
E ) tot e (k )v (k )
2 dk 3
4 3
（ Electrical Conductivit
y）
1 e （ Seebeck
S  ( fE0 ) tot e (k )v 2 (k )( E  E f ) 4dk 3
3

T Coefficient ）
tot-e(k) : relaxation times for both carrier transport.
carrier transport with scattering from phonon and impurities
included; no effective way to determine tot (k) yet.
Ab initio method to calculate tot ?
Electron scattering in crystal & composites: A very challenge work.
B. Far from equilibrium transport: still an argument.

3. Thermal transport: Thermal conductivity

 Experimental Nanothermoelectrics

Formation & microstrustural evolution of

thermoelectric nanocompsites

 Realizing homogenous dispersion of nano objects;

 Growth and evolution of nano dispersions;
 Interface-induced or interface-controlled
microstructure formation: dynamics and kinetics
 Nonequilibrium formation of nano composites;
 Size distribution and performance

Controllable synthesis of nanocomposite materials

Nano composites
 Experimental Nanothermoelectrics

Structure characterization and

property measurements
 Microstructural characterization:
3-dimensional structure
 Functionality measurements:
Inhomegeneous at atomic scale ??
 Spectroscopy measurement: Hall, D
electron conductivity, thermal O
S
transport, various other
spectrum density of states
Energy

Detailed microstructure and function characterization;

Advanced spectroscopic measurement for electronic structures.
 Research on Thermoelectrics in SICCAS
 Thermoelectric Materials
 New concepts and search for new materials: theory and expt
 Nanocomposites: nano- grained, nano- dispersion, texture, …
 Organic/inorganic composites and organic TE Materials
 TE films: Bi2S3 , Bi2Te3 etc.
 Mechanical stability improvement: doping and texture
 Mess production for industrial applications
 Thermoelectric Devices
 Waste heat recovery and cooling: automobile
 Special power generation

 Research groups invloved

Prof. Chen Lidong (composites, devices, and systems)
Prof. Zhang Wenqing (new compounds and TE material design)
A few chemistry people
 Supported by
MOST-973, NSFC, CAS, local automobile company, US-Corning, GM
 Computational Materials Physics Group
 Fundamental Research on Energy-conversion Materials
( 能量载流子的输运及其耦合：电子 - 声子 - 离子）
L Xi, Jiong Yang, W Zhang et al., J Am Chem Soc. (2009)
Jiong Yang, HM Li, WQ Zhang et al., Adv. Funct. Mater. (2008)
X.Shi, W. Zhang, LD Chen, J. Yang, Phys. Rev. Lett. (2005).
W Zhang, X. Shi, ZG Mei, LD Chen et al., Appl. Phys. Lett. (2006).
ZG Mei, W Zhang, LD Chen et al., Phys. Rev. B 74, (2006) ； Phys. Rev. B.
(2008)
YZ Pei, LD Chen, W Zhang et al., Appl. Phys. Lett., (2006).
J Yang, W. Zhang et al, Appl. Phys. Lett., (2007).
X. Shi, W. Zhang, L. D. Chen, et al., Phys. Rev. B, 75, 235208 (2007).
X Shi, W. Zhang, LD Chen, Acta Mater. (2008)
 Physics and Chemistry at Interfaces
( 界面功能性与复合材料设计：无机 - 无机界面、无机 - 有机界面 )
HT Li, W Zhang et al., Acta Mater. (2009).
J Feng, W Zhang, et al. , Phys. Rev. Lett. 97, (2006); Phys. Rev. B (2005).
W. Zhang et al., Inter. J. Mater. Sci., (2006).
W. Zhang et al., Phys. Rev. B 70, 024103 (2004); Phys. Rev. B 67, 542414
(2003).
W. Zhang et al., Phys. Rev. Lett. 85,3225,(2000); Phys. Rev. Lett. (1999).
Thank you for your attention!
International Conference on Thermoelecrics
ICT’2010, Shanghai, China
 Key scientific issue – size effects

Functions of nano dispersions: electronic Nano dispersions

structure and phonon spectrum from the localized

nano-dispersions; their effects on electrical and
thermal transports of the whole nano composites

Research:

Electron DOS
 Microstructure characteristics of nano dispersions;
 Electronic structures of composites with nano
dispersions and transport properties; effects from 3D
resonant states around Fermi level;
 Effect from the atomistic nonhomegeneous materials;
Energy (meV)
 Correlation between local properties and global
performance. Quantum Confinement effect:
Seebeck enhancement
 Key scientific issue – Interface effects

Functionality of Interfaces

Research:
 Microstructure and electronic properties of
specific interfaces;
 Interface effect on electron/phonon transport;
 Microscopic and atomistic modeling of interfaces;
 Design high performance materials based on
understanding of the effects of size and interface
on transport behavior of nanocomposites

Energy filtering effect

 Typical Energy Path in Gasoline Fueled Internal
Combustion Engine Vehicles V e h ic le O p e r a tio n
30%
E n g in e

Combustion
Gasoline
Gasoline
Gasoline

100%
25%
M o b ility &
A c c e s s o r ie s

5%
F r ic tio n &
R a d ia te d

30%
C o o la n t
GEN I
N o te : C h a rts in th is p re s e n ta tio n
40% a re d ra w n fro m m u ltip le s o u rc e s
a n d m a y h a v e slig h tly d iffe re n t
Exhaust n u m b e rs b e c a u se o f d iffe re n t
G as v e h ic le s & a s su m p tio n s . C o n s id e r
th e m g e n e ra l e s tim a te s , n o t p re c is e
a n a ly sis.
GEN II

GEN III

 Today’s ICE-based vehicles: < 20% of fuel energy is used for propulsion
 > 60% of gasoline energy (waste heat) is not utilized
Distributed Cooling for High Efficiency HVAC
System
 Reduce onboard AC without sacrifice passenger comfort level
 Improve fuel economy and CO2 emission
 DOE award in place to start in 2009

“If all passenger vehicles had ventilated

seats, we estimate that there could be a 7.5
% reduction in national air-conditioning fuel
use. That translates to a savings of 522
million gallons of fuel a year,"
John Rugh, project leader for NREL's Vehicle Ancillary
Loads Reduction Project.
 Exhaust Generator GEN III Design
 Located where current muffler is placed; new
Interior View TE Exhaust muffler will be located behind the axle perpendicular
(module mounting) Generator to vehicle axis
 Axially compliant for thermal expansion mismatch
Case 08

TE Exha ust
Genera tor

 Maximum module compression compliance

 Quick disconnects for fluid flow
 Quick disconnect exhaust connections
 Pitched to drain condensate
 Pitch designed for boil off
 Sealed electronics
FFL and Electronegativity-based Selection Rule

Point ： What controls the filling fraction limit

？

Ca Ba La Ce Yb  A stable filled CoSb3 has to

Exptl satisfy an electronegativity-
0.20 0.44 0.23 0.10 0.19 based selection rule:
FFL

 Competition between the filled

phase and possible secondary
phases determines the FFL. x: Electronegativity of atom.

Shi, Zhang*et al, Phys. Rev. Lett.

FFL: Theoretical predictions
(2005).
agree well with
Shi, Zhang*et al, experimental
Phys. Rev. B. (2007).
data.
Shi, Zhang*et al, Acta Mater. (2008).
 The Electronegativity-based Selection Rule
The x-based selection rule(x =xSb － xI >0.80):
 Most of atoms form no stable filled phase ；
 RE and AE atoms do form stable filled phases;
 AM-filled CoSb3 － novel filled phases ？

Novel filled
CoSb3 ？
Alkali-metal-filled skutterudites: Na yCo4Sb12 and KyCo4Sb12

Na0.43Co4Sb12
(n-type)
ZT

 Na and K has a maximum filling fraction (up to 65%) reported.

 NayCo4Sb12 shows the highest power factor and ZTs among all single
filled SKTs.

AM-filled CoSb3: 2007 Goldsmid Award (Dr. Pei YZ); 29

Pei, Chen, Zhang, APL (2009,2007); Mei, Zhang, Chen, PRB (2007).
 Optimal Combinations of multiple fillers
Optimal Combinations of multiple fillers :
“Using fillers with largely different
rattling frequencies to realize wide-
异种填充原子选择规则的指导意义：
spectrum phonon scattering, especially
for the low-frequency phonons ”

Filler Rattling
atom 0 (cm-1)
La 68  Bad combinations ：
稀土 Ce 55 REs （ Mischmetal ）
（ RE ）
Eu 59 AEs （ Ba ＋ Sr ）
Yb 43  Good combinations ：
碱土 Ba 94 Dual ： Ba +Yb , Ba + Ce ，
（ RE ） Sr 91 Yb + Na ，…
碱金属 Na 113 Triple ： Yb + Ba + Na , …
（ AM ） K 142
 ZTs of the Ba-Yb dual-filling CoSb3

Ba0.08Yb0.09Co4Sb12 Na0.43Co4Sb12 Ba-Yb dual-filled CoSb3

(n-type)
(n-type)
reaches ZT~1.36@850K,
Best among the CoSb3-
热电性能优值

based bulk materials ！

ZT

(2008)

A series of dual-filled
CoSb3 (~ 1.4@850K)
could be obtained
easily.

Yang, Zhang, Chen et al, Appl. Phys. Lett. 91, (2007)

Shi, Yang, Chen, Zhang, Uher* et al, Appl. Phys. Lett. 92, (2008)
US patent - with GM, 2008 ， #61036715
 Rattling Frequency:
Calculations vs Inelastic Neutron Scattering Experiment

Yb Eu Ba

La
• Calculated resonant phonon frequencies are experimentally validated

5
 多填充方钴矿的性能优化
Range of optimal carrier density

0.0 0.1 0.2 0.3 0.4 0.5

Total Filling Fraction
AxByCzCo4Sb12

X. Shi, Jiong Yang, W. Zhang, Jihui Yang et al., to be submitted

 Carrier scattering mechanisms in TE materials
 Lattice scattering
Intravalley: Acoustic – deformation potential
Acoustic – piezoelectric
Optic – polar
Optic – nonpolar
Intervalley: Acoustic and optic phonon
 Defect scattering: impurity – neutral
impurity – ionized
large impurity – boundaries, precipitates,…
 Carrier – carrier scattering: …

1. Only a few of them can be dealt with from the bottom of theory;
2. The same argument also applies to the study of thermal transport of TE
materials (phonon transport problem).
 Computational
电热输运理论研究 Thermoelecrics

Rational Search for novel thermoelectric compounds:

 Ab initio understanding of the functionality of the key
structural unit;
 Exact e-ph scattering from ab initio for relatively quantitative
prediction of transport properties

  e  (2 f 0
E ) tot e (k )v (k )
2 dk 3
4 3

1
  (1  cos kk ' )[P e  ph (k , k ',  )  P defect (k , k ',  )  ...]
 (k ,  ) k ',
Thermal conductivity from equilibrium MD simulations

Green-Kubo formula
The G-K formula for the thermal conductivity is:

1  Heat current
κ
Vk BT 2 0
 J (t )  J (0) dt correlation function

j
The heat current can be expressed as:

1 N  1 N

J(t)    i Ei   rij   Fij i    i
V 2 vi
 i 1  j 1, j i  
Single particle convection SiC-based nanocomposite

Long running time; Average over results for several different MD runs.