Journal of Alloys and Compounds 655 (2016) 321e326

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Synthesis, characterization and thermoelectric properties of Sm lled

Fe4
xNixSb12 skutterudites
Riccardo Carlini a, b, *, Atta Ullah Khan c, Riccardo Ricciardi a, Takao Mori c, d,
Gilda Zanicchi a, b
a

Chemistry and Industrial Chemistry Department, University of Genoa, Via Dodecaneso 31, Genova, Italy
INSTM e Interuniversitary Consortium of Science and Technology of Materials, UoR Genoa, Italy
International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba 305-0044, Japan
d
Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba 305-8671, Japan
b
c

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 6 March 2015
Received in revised form
9 September 2015
Accepted 15 September 2015
Available online 25 September 2015

High gure of merit of n-type skutterudites have encouraged the researchers to focus on its p-type
counterpart. In the following study, we report a rather simple synthesis route for Sm lled and Ni-doped
p-type skutterudites (SmyFe4
xNixSb12.8, y 0.7e0.8, x 0.4e1.2, nominal composition), along with
high temperature thermoelectric properties. Sample were prepared by melting, quenching, followed by
annealing and the resulted chunks were cut into disks form to measure the thermoelectric properties
without applying high pressure sintering techniques. Ni addition helped in optimizing the carrier concentration and resulted in a nal ZT of 0.55 at 560 K.
2015 Elsevier B.V. All rights reserved.

Keywords:
Filled skutterudites
Advanced thermoelectric materials
Intermetallic compounds
Synthesis routes

1. Introduction
Today, the general energy shortage leads us to investigate
different elds in order to search for new energy sources or energy
saving pathways. Thermoelectricity is an attractive technology for
generating electrical power directly from waste heat. The devices
based on thermoelectric technology could play an important role in
the future global requirement of energy due to their dual role in
power generation and in refrigeration [1e3]. This thermoelectric
energy approach relating to the fundamental issues of sustainability and eco-environmental compatibility can be employed in
different areas: aerospace applications, automotive eld, and
nautical freight etc.
The efciency of a thermoelectric material is related to a
dimensionless quantity, the gure of merit (ZT)

ZT

S2 s
T
k

* Corresponding author. Chemistry and Industrial Chemistry Department, University of Genoa, Via Dodecaneso 31, Genova, Italy.
E-mail address: riccardo.carlini@unige.it (R. Carlini).
http://dx.doi.org/10.1016/j.jallcom.2015.09.141
0925-8388/ 2015 Elsevier B.V. All rights reserved.

where T denotes the absolute temperature, S is the Seebeck coefcient, s the electrical conductivity and k the total thermal conductivity. A good thermoelectric material is characterized by a high
Seebeck coefcient combined with a high electrical conductivity
and a low thermal conductivity. k is constituted by an electronic
contribution ke, directly related to s via the Wiedemann-Franz law,
and a lattice contribution kl: a decrease of kl could lead to a
decrease of k without reducing S2s term [4e7].
Numerous intermetallic compounds could be considered as
good candidates for thermoelectric applications; a particular interest has been devoted to the transition metal antimonides (Zintl
phases, clathrates, skutterudites, etc.) [8e16].
Skutterudites attracted great interest for decades due to their
relative low-cost and promising thermoelectric performance as
possible candidates for thermoelectric power generation at middle
temperature range [17]. Both n- and p-type skutterudites are
necessary in the design of TE modules. N-type skutterudites show
higher ZTs than the p-type ones due to their large effective masses
and high power factors. Therefore it is very important to improve
the TE performances of p-type skutterudites above all, in terms of
Seebeck coefcient and thermal conductivity. Typically p-type
skutterudites originate from the binary compound CoSb3 after
partial/total substitution of Co with other transition metals such as

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R. Carlini et al. / Journal of Alloys and Compounds 655 (2016) 321e326

Fe [18,19]. Rare earth elements are employed as llers which increase the electrical conductivity by donating 2 or 3 electrons per
atom with a consequent increase of structure stability, and also
suppress the thermal conductivity due to rattling. But the limited
lling fraction in Fe/Co compounds cannot effectively lower the
hole fraction: addition of Ni atoms could overcome this problem.
Different researches indicate that the Ni substitution could help in
optimizing hole concentration leading to higher ZTs [20e22].
Theoretical studies reveal that the valence band of these skutterudites consists of 5p-state for Sb and 3d-state for the transition
metal: this condition could be inuenced by either Co or Ni substitution. Recently this behaviour has been the subject of deepened
studies, but its understanding is still far from the answer.
In this work, Fe and Ni based skutterudites are obtained as bulk
samples by quick and cheap synthesis and a chemical-physical
characterization is carried out. Sm was chosen as the ller due to
its dual valence: Sm2 and Sm3. This property could justify the
presence of divalent or trivalent cations in skutterudites leading to
an increasing electronic stability together with an improvement of
the TE performances [22e24].
2. Materials and methods
A very similar route to the state of the art synthesis reported for
FeeCo and FeeNi based skutterudites was carried out [25e28]. In
particular, the proposed synthesis provided an unlled skutterudite
(Fe, Ni)4Sb12 which then was lled with Sm.
Starting with iron (rod by Alfa-Aesar: 99.99 mass %), antimony
(ingot by Mateck: 99.999 mass %), nickel (foil by Mateck: 99.99
mass %) and samarium (rod by NewMet: 99.9 mass %), small pieces
of the stoichiometric quantities of elements were sealed in silica
ampoules under Ar ow.
Then, the desired amount of samarium was added in the obtained ternary skutterudites and subjected to a thermal cycle: a
second melting in a mufe furnace at 1273 K, followed by a quick
melting in the induction furnace, to promote the sample homogenization, and an annealing at 903 K for 7 days. The samples thus
obtained are labelled as SKUT series.
The preliminary analysis carried out revealed that the key points
to get lled single phase skutterudites were the rapid cooling and
annealing temperature.
In order to reduce time and costs of synthesis, according to the
rst results, a different synthesis route was proposed. Starting
directly from the four elements, the samples were heated at 1273 K
in a mufe furnace for 3 h and rapidly quenched in salt water and
ice.
In literature, there is no information about the peritectic temperature for the quaternary SmyFe4
xNixSb12; nevertheless,
assessing the phase diagrams of similar skutterudites, 873 K was
reasonably adopted as annealing temperature to stay for sure
below the peritectic temperature.
Therefore, the samples were annealed for 60 h at 873 K and air
quenched. This synthesis provided a signicant reduction in terms
of number of steps, annealing times and, consequently, production
costs.
The samples obtained through this route are labelled as SKT
series.
The nominal content of Ni (x) in each series was x 0.4, 0.8 and
1.2 and such number was used labelling the series, so that SKT 0.4 is
referred to the SKT sample which Ni content is x 0.4, and so on.
Scanning Electron Microscopy (SEM) equipped with Energy
Dispersive X-ray Spectroscopy (EDXS) and X-ray diffraction (XRD)
analyses were used to examine microstructures and determine
phase composition of bulk samples. A scanning electron microscope EVO 40 (Carl Zeiss) was employed, equipped with a Pentafet

Link (Oxford Instruments) detector for EDXS analysis. Smooth

surfaces for microscopic observation were prepared by using SiC
papers and diamond pastes with grain size down to 1 mm. For the
quantitative analysis, an acceleration voltage of 20 kV was applied;
a cobalt standard was used for calibration. The X-ray spectra were
processed by the software package Inca Energy (Oxford Instruments). X-ray diffraction analysis was used to identify the
phase crystal structures and determine the lattice parameters. The
measurements were performed on powdered samples (obtained by
grinding parts of chunks) mounted on a zero background Si support, by means of a vertical diffractometer (Philip X'Pert model). Xray patterns were recorded using the Cu Ka radiations in the
19e100 2q angular range, with a step of 0.013 and a counting time
per step of 30s. A 40 kV voltage and a 30 mA current were applied to
the X-ray tube. Lattice parameters were calculated and rened by a
least-squares routine, and compared with literature values. Data
renement was carried out using Rietveld method by FullProf Suite
software. To determine thermal conductivity, obtained chunks after
synthesis, having 12 mm diameter and 20 mm length roughly, were
cut into round discs with diameter close to 10 mm by using diamond saw. Platinum wire based thermocouples were attached on
these discs with silver paste to measure 1/Dt (where t stands for
temperature). The thermal diffusivity coefcient and relative specic heat were measured by the laser ash method (ULVAC
TC7000). As the absolute specic heat value at 300 K, the value
from a reference sample measured by Physical Properties Measurement System (PPMS, Quantum Design) was used. Rectangular
rods after cutting these discs with size of 2*2*8 mm3 were used for
electrical transport measurement. Resistivity and the thermoelectric power were measured simultaneously with an ULVAC ZEM-2
under a low pressure inert gas (He) by using the four probe
method. Measurements temperature ranges from 300 K to 750 K
with some unavoidable differences between the resistivity and
thermoelectric power measured temperatures and the thermal
conductivity measurements. To estimate the ZT, the thermal conductivity data was tted to obtain the values matching the resistivity and thermoelectric power measurements.
3. Results and discussion
The skutterudites belong to the body-centred-cubic Im3 space
group; only six of the available 8 small cubes are lled by a ring of
Sb, meanwhile the other two could host different llers.

Fig. 1. Diffraction patterns of samples belonging to the SKUT series compared to the
Fe2Ni2Sb12 [29].

R. Carlini et al. / Journal of Alloys and Compounds 655 (2016) 321e326

323

Table 1
Nominal and SEM-EDXS samples compositions.
Code

Sample

Composition (at.%)
Nominal

SKUT 1.2
SKUT 0.8
SKUT 0.4
SKT 1.2
SKT 0.8
SKT 0.4

Fig. 2. Plot of lattice parameters with respect to Ni content (x). Increasing Ni content
decreases lattice parameters.

Powder X-ray diffraction was carried out on the prepared SmyFe4
xNixSb12 samples at room temperature to obtain lattice parameters and their dependence on x. All diffraction patterns show
almost single phase samples where the prevalent phase is the
skutterudite together with a very low amount of Sb. Furthermore,
no signicant differences can be observed between the two series
studied in terms of lattice parameter values and number of phases.
In Fig. 1, the diffraction patterns of the SKUT series are displayed.
Diffraction patterns reveal a good agreement of the experimental lattice parameters with those reported in literature for the
similar compounds [4,21,29e31].
Fig. 2 shows the trend of lattice parameters depending on x: a
linear dependence could be observed, according to the Vegard's
law. Small size Ni (as compared to Fe) results in shrinkage of the
lattice.
Morphological and compositional data of the investigated
skutterudites, obtained by SEM-EDXS, indicate that all as cast
samples can be considered as almost single-phase. Fig. 3a and b
displays microphotographs of SKUT 1.2 and SKT 1.2, obtained by the
Back Scattered Electrons (BSE), as a representative of all the samples. The dominant phase is the skutterudite; a little amount of
antimony can be observed in Fig. 3a. The dark numerous dots show
the porosity of bulk samples, which is understandable in the
absence of any high pressure technique. Within the largest of these
holes, well-formed crystals of quaternary skutterudite can be
observed. A beautiful cubic crystal is shown in Fig. 3c obtained by

Sm0.7Fe2.8Ni1.2Sb12.8
Sm0.7Fe3.2Ni0.8Sb12.8
Sm0.8Fe3.6Ni0.4Sb12.8
Sm0.7Fe2.8Ni1.2Sb12.8
Sm0.7Fe3.2Ni0.8Sb12.8
Sm0.8Fe3.6Ni0.4Sb12.8

SEM-EDXS

Fe

Ni

Sb

Sm

Fe

Ni

Sb

Sm

16.0
18.3
20.4
16.0
18.3
20.4

6.9
4.6
2.3
6.9
4.6
2.3

73.1
73.1
72.7
73.1
73.1
72.7

4
4.0
4.5
4
4.0
4.5

16.5
18.5
20.5
16.3
18.7
20.3

6.9
4.6
3.9
7.1
4.4
2.2

73.5
73.4
72.2
73.5
73.2
73.1

3.1
3.5
3.4
3.1
3.7
4.4

using Secondary Electrons (SE).

The compositions of samples are reported in Table 1. Both series
show a good agreement between the EDXS compositions and the
nominal ones.
Table 2 shows the measured densities of the samples and those
calculated by the Rietveld renement of the XRD patterns. It can be
observed that all samples have similar densities but smaller than
the theoretical ones; conrming that the synthesis carried out in
the absence of high pressures favour the formation of cavities with
a consequent lowering of the density.
The temperature dependent electrical and thermal conductivity
for SmyFe4
xNixSb12 samples are shown in Figs. 4 and 5 respectively. For the samples having the lowest Ni amount, electrical
conductivity declines with increasing temperature in accordance
with a typical metallic behaviour. Only in the case of the
Sm0.7Fe2.8Ni1.2Sb12.8 samples, they show a very small decrease of
the electrical conductivity till 370 K and a stronger increase with
increasing temperature thereafter. A similar behaviour is reported
by Tan et al. and Goldsmid [21,33] and justied by the intrinsic
excitation of electron-hole pairs across the energy gap. In general,
increasing Ni content degrades the electrical conductivity by
neutralizing some of the holes, hence decreasing carrier concentration [21]. Although, SKT 0.8 differs, it could be due to the high
porosity of the sample (Table 1). The electrical conductivity values
in general, are in good agreement with the literature data
[17,21,25,26,32].
All samples show an overall rise in thermal conductivity with
increasing temperature. However, there is a drastic change at
elevated temperatures most probably due to the bipolar diffusion
[21]. In general, Ni addition suppresses the thermal conductivity,
due to two reasons, (1) by phonon scattering from lattice distortions caused by the different atomic size of Ni from Co, and (2), due
to the lowering electronic contribution of thermal conductivity
because of degradation in electrical conductivity. The thermal
conductivity values (Fig. 5) are comparable with the literature data

Fig. 3. a) BSE-SEM micrograph of SKUT 1.2; b) BSE-SEM micrograph SKT 1.2. Skutterudite phase is the dominant phase (dark grey), a very little amount of antimony (light grey) can
be observed in SKUT 1.2; c) SE-SEM micrograph of a cubic crystal of SKT 1.2.

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R. Carlini et al. / Journal of Alloys and Compounds 655 (2016) 321e326

Table 2
Measured and calculated densities of the samples.
Sample

Measured density

Calculated density

Densities ratio

SKUT 1.2
SKUT 0.8
SKUT 0.4
SKT 1.2
SKT 0.8
SKT 0.4

6.25
6.12
6.47
7.05
6.14
6.27

7.63
7.77
7.54
7.68
7.78
7.70

0.82
0.79
0.86
0.92
0.79
0.81

[17,21,25,26,32]. Although, a bit higher slope could be observed in

the present study as compared to the similar ones reported in
literature.
Positive Seebeck coefcients (S) for all samples (Fig. 6) in the
entire temperature range indicates holes as the majority charge
carriers. These values are slightly higher than the ones reported in
literature [17,21,25e27,32]. Furthermore, the samples having a low
Ni content show a continuous increase of S roughly up to 700 K,
where a peak value (Smax) is observed. Increasing Ni content affects

the Smax and it is shifted towards lower temperatures; thereafter a

strong slope is shown by the x 1.2 curves. This behaviour is in
agreement with Kaltzoglou et al. [28] and to some extent with Tan
et al. [21] and is justied by the electrical conductivity trend previously discussed. Overall, Ni addition plays a positive role in
enhancing the Seebeck Coefcient at lower and middle temperatures but the difference diminishes at higher temperatures, most
likely due to the intrinsic electron excitations and quite similar to
the one reported in literature [21].
Fig. 7 displays the gure of merit ZT values as a function of
temperature for all the investigated samples. Higher Ni content
seems to enhance the ZT. However, increasing Ni amount shifts the
maxima of ZT towards lower temperatures. This behaviour could be
considered positive owing to the highest efciency of these skutterudites observed at lower temperature than the ones reported in
literature [17,21,25e27,32]. However, these values are rather lower
than the ones reported by Rogl et al. and Zhang et al. [25,32] but
quite similar to the ones reported by Tan et al. [17,21]. Highest ZT of
0.55 was observed with x 1.2 at ~560 K. A more important aspect
of the present work is the high average ZT of SKUT 1.2 sample below

Fig. 4. Temperature dependence of the electrical conductivity for different values of Ni concentration.

Fig. 5. Temperature dependence of the thermal conductivity for different values of Ni concentration.

R. Carlini et al. / Journal of Alloys and Compounds 655 (2016) 321e326

325

Fig. 6. Temperature dependence of the Seebeck coefcient for different values of Ni concentration.

Fig. 7. Temperature dependence of the gure of merit (ZT) for the samples with different values of Ni concentration.

600 K with a room temperature value exceeding 0.3. It is evident

from these results that we can tune the maxima of ZT by controlling
Ni content and it is possible to alter this material according to the
required temperature range.
The samples obtained through the cheaper and faster synthetic
route (SKUT series) show a better performance than the other ones
(SKT series). A processing such as Spark Plasma Sintering or Open
Die Pressing could lead to higher values than the ones observed in
this study by improving the overall density of the samples.

The increasing Ni content leads to a lower electrical conductivity

typical of semiconductive materials, while an improvement in
Seebeck coefcient is observed. Thermal conductivity is hardly
inuenced by the Ni content. The resulting gure of merit ZT could
be considered slightly lower than the ones reported in literature.
The best performance is observed for Sm0.7Fe2.8Ni1.2Sb12.8 sample
having the highest ZT 0.55 at ~560 K. This study shows that a
selection of appropriate llers, and optimization of carrier concentration through adjustment of Ni content could further improve
the thermoelectric properties of these p-type skutterudites.

4. Conclusions
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shown by SEM-EDXS investigation, having compositions quite
consistent with the nominal ones. The lattice parameters reveal a
good agreement with the ones of similar compounds reported in
literature; their trend with the Ni content respects the Vegard's law.

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