Progress in Natural Science: Materials International 2012;22(3):201–206

Chinese Materials Research Society

Progress in Natural Science: Materials International

www.elsevier.com/locate/pnsmi
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ORIGINAL RESEARCH

Preparation of nano-sized Bi2Te3 thermoelectric material

powders by cryogenic grinding
Xiaozong Chena, Leifeng Liub, Yuan Donga, Lianjun Wanga,n,
Lidong Chenc, Wan Jianga,n

a
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, 2999 people of North Road,
Shanghai 201620, PR China
b
Department of Materials and Environmental Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden
c
Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, PR China

Received 19 November 2011; accepted 29 March 2012

Available online 13 June 2012

KEYWORDS Abstract A novel method for rapid preparation of Bi2Te3 nano-sized powders with an average
Thermoelectric (TE)
particle size of about 70 nm was developed. A starting powder mixture consisting of Bi2Te3 coarse
material; particles of 5 mm was ground using cryogenic grinding in the liquid nitrogen. For comparison,
Cryogenic grinding; the conventional high-energy ball milling was used to prepare the Bi2Te3 nano-sized powders.
Bi2Te3; Sintering properties of as-prepared powders was investigated by spark plasma sintering (SPS). The
Nanoparticles; effects of the preparation procedure on the crystallinity, morphology and structure were examined
Two-step breaking by X-ray diffraction (XRD) and transmission electron microscopy (TEM). It was found that Bi2Te3
model was not transformed into a non-equilibrium amorphous phase or decomposed during the cryogenic
grinding process, and as-prepared nano-powders possessed excellent sinterability. This technique
might also be applicable to other thermoelectric materials.

& 2012 Chinese Materials Research Society. Production and hosting by Elsevier Ltd. All rights reserved.

n
Corresponding authors: Tel.: þ86 21 67792835; fax: þ86 21 67792855.
E-mail addresses: wanglj@dhu.edu.cn (L. Wang),
wanjiang@dhu.edu.cn (W. Jiang).
1002-0071 & 2012 Chinese Materials Research Society. Production
and hosting by Elsevier Ltd. All rights reserved.
Peer review under responsibility of Chinese Materials Research
Society.
http://dx.doi.org/10.1016/j.pnsc.2012.04.006
1. Introduction
Thermoelectric (TE) material with the function of the direct
solid-state conversion between thermal and electrical energy
has received enormous attention in the past twenty years
because of its potential on the application of eco-friendly
energy, cooling and space energy source [1,2].
In the TE family group, Bismuth telluride (Bi2Te3) and its
alloys, discovered by Loffee in the early 1960s, are the most
widely applied TE materials over the temperature range
200–400 K, due to the high TE performance [3]. The Bi2Te3
crystal has a hexagonal structure that consists of quintuple
atomic layer series in the order of Te(1)–Bi–Te(2)–Bi–Te(1)
202
along the c-axis [4,5]. Since Te(1)–Te(1) layers are weakly
bonded by the van der Waals forces, this crystal can easily
cleave on the basal plane resulting in some difficulties for
large-scale application [6].
Since the American scientist Dresselhaus [7–9] put forth the
issues that low-dimension and nanostructure can significantly
enhance the thermoelectric performance in 1990s, a lot of work
has been done to fabricate the nanoparticles [10–16] and
nanocomposites [17–19] by many researchers. Among those, a
simple approach employing ball-milling of bulk BiSbTe alloy
and subsequent hot pressing has been reported to be effective
for producing the nanoparticles with average grain size of
20 nm [10]. This method is also cost-efficient, which means that
it is promising in large-scale application. However, the conven-
tional grinding inevitably generates a large amount of heat that
causes the lattice distortion and the breaking-down of chemical
bonds, making the material amorphous or decomposed [20].
Thus, it is desirable to further develop a method which can be
used to produce the nanoparticles and at the same time
introduce fewer amorphous phase and decomposition.
Cryogenic grinding (CG) is always called ‘‘Mill of last
resort’’. Since the cryogenic medium, always the liquid nitrogen,
Fig. 1 XRD patterns of (a) the ingots and the particles CGed for different times and (b) the particles after 12 h, 24 h, 36 h and
60 h HEBM.
X. Chen et al.
provides an extremely low temperature of 195.6 1C and an
inert atmosphere, it prevents the amorphous transition and
decomposition of the substance [21–24]. Meanwhile, the low
temperature provided by cryogenic precooler is below the brittle
point of most materials, which makes the grinding process more
efficient. Therefore the cryogenic grinding is considered as the
best milling method for these hard grinding samples and the
substances susceptible to oxidation and volatile.
In this paper, both cryogenic grinding and conventional
high-energy ball milling (HEBM) were employed for grinding
N-type Bi2Te3 particles. The microstructure feature of
Bi2Te3 powder after the CG and HEBM was investigated
and compared.
2. Materials and methods
The starting material of N-type Bi2Te3 zone-melted ingots was
from a commercial supplier (Shenhe Thermo-Magnetics Co.
Ltd., Shanghai, China). The ingots were crushed into coarse
particles of 5 mm by steel mortar. Then the coarse particles
Preparation of nano-sized Bi2Te3 thermoelectric material powders by cryogenic grinding 203

were milled to fine powder by either cryogenic grinding or
high-energy ball milling.
The crushed sample was grinded by a CG machine (SPEX
SamplePrep 6770 Freezer/Mill, TECH-Knowledge Interna-
tional Co., California, USA). The sample and a magnetically
driven impactor were inserted into a closed grinding vial
immersed in liquid nitrogen and precooled to make Bi2Te3
below its brittle point. The grinding was performed for a few
minutes at the speed of 10–12 cycles per second. During the
process, the grind was paused every 2 h to collect a small
amount of the powder for analysis and post treatment.
The same crushed sample was also milled in a HEBM
machine (Model GN-2, Shenyang Science Equipment Factory,
Shenyang, China) at the speed of 480 rpm using a steel vial.
The steel vial was sealed in a glove box under argon atmo-
sphere. The as-prepared Bi2Te3 nano-powders were sintered
using spark plasma sintering (SPS, Dr. Sinter 725, Sumitomo
Coal Mining Co., Japan). The nano-powders were loaded into
cylindrical carbon dies with an inner diameter of 10 mm. The
heating rate was controlled in the range of 70 1C/min, and the
pressure was set at 60 MPa. The final temperature was selected
at 390 1C for a dwelling time of 5 min, respectively.
The as-prepared powders were analyzed by X-ray diffraction
(XRD) with Cu Ka radiation at 40 kV and 100 mA. The
particle morphology and microstructure observation were
performed by transmission electron microscopy (TEM). After
sintering, the surfaces of samples were ground to remove the
graphite layer. The densities of consolidated specimens were
obtained using the Archimedes immersion method with deio-
nized water as the immersion medium. The theoretical densities
of the specimens were calculated according to the rule of
mixtures. Microstructural observation was conducted using a
scanning electron microscope (FE-SEM: JSM-5600LV, JEOL,
Japan).
3. Results and discussion
The XRD patterns of uncrushed Bi2Te3 ingots and the grinded
samples by CG for different time are shown in Fig. 1(a). The
diffraction peaks cited from the database of binary Bi2Te3
(PDF#15-0863) were plotted at the bottom of the figure with
vertical lines. The strong peaks of (0 0 3), (0 0 6) and (0 0 15)
in the pattern of raw ingots indicate the existence of texture in
the material. The texture disappeared as the ingots were
grinded into fine powder, which made those peaks weakened
dramatically. Owing to the hugely anisotropic structure with
lattice parameters a ¼0.438 nm and c ¼3.049 nm [4], and
Te–Te layers are weakly bonded by the van der Waals forces
along with c-axis, the resistance of the Bi2Te3 ingots to shear
on non-basal planes is much greater than that on basal planes
[5]. During milling process, much more dislocations occurred

Fig. 2 Low- resolution TEM images of the particles CGed for (a) 3 h, (b) 6 h, (c) 10 h and (d) 15 h with the corresponding electron
diffraction pattern and high-resolution TEM images of the particles after (e) 10 h and (f) 15 h CG.
204 X. Chen et al.

on the basal plane than those occurred on the non-basal plane

leading to the break-down of the long-range lattice order in
the direction of c-axis [6], which is also confirmed in the high
resolution TEM image, as shown in Fig. 2. As a result, the
XRD reflections of the basal plane weakened and even
disappeared.
The reflections were weakened and broadened severely until
the milling time of 10 h, which indicated the continuous
decrease in crystal size. The XRD pattern of 15 h milling
had the similar peak width and intensity as the 10 h milling
one, indicating that the further milling beyond 10 h made no
more changes on the crystal size. After 15 h extensive milling
under CG, no extra peak or peak shift can be found in the
XRD pattern, indicating that no phase transition happened
during the milling. Moreover the background of pattern after
15 h milling was still flat and low. This means that the CG
process successfully restrained the generation of amorphous
phase and chemical decomposition.
Fig. 1(b) shows the XRD patterns of Bi2Te3 powder after
different HEBM time (the increment between any adjacent
XRD pattern remains in line with Fig. 1(a)). It can be found
that all the characteristic peaks of HEBMed powder coincided
well with those of Bi2Te3 and the shape of peaks keeps
unchanged with the increase of the HEBM time (60 h),
indicating that the Bi2Te3 particles display ductility perfor-
mance just like metal and are hard to grind to nanoparticles.
This can be seen obviously in the TEM image in Fig. 3. In
addition, it is inevitable to introduce an amount of impurities
after long time ball milling.
The microstructures of Bi2Te3 particles after CG for
different times are shown in TEM images in Fig. 2. The low
resolution TEM images of 4 h and 6 h CGed sample (Fig. 2a
and b) show that the average particle size remains about
200 nm, and varies barely before the 6h. However, as the
grinding continued, the average particle size decreased
obviously from the 6 h. The TEM images of 10 h and 15 h
CGed sample (Fig. 2c and d) show that the average particle
size decreases dramatically to about 70 nm. Interestingly, the
results of high resolution TEM (Fig. 2e and f) clearly reveal
the existence of 10 nm nanocrystals in different orientation
inside of particles. The further grinding will not decrease the
particle size significantly. This means that the major break-
down process occurred from 6 h to 10 h, and the particle size
reaching the minimal size of about 70 nm maintained even
prolonging the grinding time. The selected-area electron
diffraction (SAED) pattern (Fig. 2c, inset) confirms the crystal
structure of Bi2Te3. In the high resolution TEM image, the
lattice frame of nano-sized Bi2Te3 particle can be clearly
observed. As marked in the image, the distance of 0.322 nm
indicates crystal plane of [0 1 5].
Fig. 3a–c show the TEM images of high-energy ball milled Fig. 3 TEM images of the particles HEBMed for (a) 12 h,
Bi2Te3 powder for milling periods of 12 h, 24 h and 36 h, (b) 24 h and (c) 36 h.
respectively. The average size of the Bi2Te3 powders remained
unchanged at about 500 nm with the increasing milling time
from 12 h to 36 h, which indicates that high-energy ball milling the milling tome of 12 h it is impossible to obtain much finer
cannot break down the micron powders. In the Bi2Te3 ingots, particles with longer ball-milling time, but it may be inevitable
the Te and Bi atoms are connected by a strong bond, either to introduce impurities and generate amorphous phase.
covalent or mixed covalent and ionic [5], and Te–Te layers are In the early time of 1920, Griffith has set up the Griffith
weakly bonded by the van der Waals forces [6], and hence, the breaking theory (GBT), which attributed the macroscopic
Bi2Te3 alloy micron particles possess weak ductility perfor- break-down of material to the microscopic crack extension
mance by the distortion and slippage of grain boundaries and [24]. On the basis of GBT, we present a two-step breaking
defects, and are hard to be grinded further. Therefore, after model to study Bi2Te3 grinding process in the present
Preparation of nano-sized Bi2Te3 thermoelectric material powders by cryogenic grinding 205

investigation. In the CG process, two dramatic break-down of
the particles occurred, as shown in the schematic diagrams of
Fig. 4a. Before the grinding, the particle size of coarse Bi2Te3
particles was about 5 mm. A large amount of microcracks in
the coarse grains and the aforementioned hugely anisotropic
structure accelerate crack extension. As a result, at the initial
stage of CG, the average particle size decreased rapidly to about
several hundred microns at the impact load within a short time,
as shown in the front part of Fig. 4a A serious brittle fracturing
of the powders occurred in the first period just like the general
milling. As is well known, the capacity of the grain distortion
and dislocation slip decreases sharply at ultralow temperature.
Since in the present study the cryogenic medium adopted was
the liquid nitrogen (195.6 1C) in the CG process, the defects of
the micron Bi2Te3 particles formed new microcracks slowly
under the severe cyclic load of 1200–1400 beats per minute, and
then further crack extension occurred during long time cycles.
Finally, the micron Bi2Te3 particles broke down into small sized
powders. This break-down mode could be named as fatigue
fracture in this period, as shown in the latter part of the Fig. 4a.
Fig. 4b shows the changes of particle size with milling time
at two breaking model. Both of the general breaking model
and the two-step breaking model present brittle fracture
within a short grinding time. In the general milling process,
with the increase of grinding time, a large part of the heat
generated during milling process makes the Bi2Te3 particles
easily to be distorted as well as the slip of the grain boundaries
and dislocations, and hence there is no second breaking down
process compared with cryogenic grinding.
In order to investigate the sintering behavior of Bi2Te3
powders prepared by cryogenic grinding and high-energy ball
milling, spark plasma sintering was used to densify as-
prepared Bi2Te3 powders at 390 1C for a dwelling time of
5min. Fig. 5 shows FE-SEM image for typical fracture surface
of bulk samples prepared by SPS at 390 1C, respectively. It is
easy to find that there are two distinct types of grains: one is
ball shape and the other is laminate shape. It was observed
that the average grain sizes of the two bulk samples fabricated
at the same sintering temperature of 390 1C were obviously
different, and the grain size of bulk sample using HEBM (b)
powders is many times larger than that using CG powders (a).
It is suggested that the cryogenic grinding is conducive to
obtain the finer nanoparticles, and then to form uniform
nanocomposite.

Fig. 4 (a) Schematic of the break-down from micron to millimicron during the CG process. (b) Milling time dependence of average
particle size of the CG samples as compared with that of the HEBM sample.

Fig. 5 FE-SEM image of bulk samples using (a) 10 h CG powders and (b) 60 h HEBM powders as precursors at sintering temperature
of 390 1C.
206
4. Conclusions
1) Bi2Te3 nano-sized powders with an average particle size
of about 70 nm were successfully prepared by a cryogenic
grinding (CG) in the condition of liquid nitrogen. The
Bi2Te3 powders showed great stability during GC process,
and no phase transformation or amorphous state was
observed to take place even after milling for 15 h. The
two-step breaking model of Bi2Te3 powders was proposed
to explain the CG process.
2) Compared with high-energy ball milling (HEBM), spark
plasma sintering (SPS) showed that cryogenic grinding
(CG) can produces much finer and good sinterability
Bi2Te3 powders.
3) This investigation presents a promising method to pre-
pare thermoelectric material nanopowders. And this
method may be used to fabricate other metal nanopow-
ders with a similar manner.
Acknowledgments
Foundation item: Projects (10JC1400500) supported by the
Shanghai Committee of Science and Technology, ‘‘Shu
Guang’’ project supported by Shanghai Municipal Education
Commission and Shanghai Education Development Founda-
tion (no. 11SG34), Projects (NCET-10–0323) supported by the
Program for New Century Excellent Talents in University; the
Fundamental Research Funds for the Central Universities and
Projects supported by Shanghai Leading Academic Discipline
Project(B603).
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