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Proceedings Visual-JW 2016 (Int. Symp. Visualization in Joining & Welding), Osaka (2016), Vol. 3, p.

7-8
in conjunction with 1st Int. Symp. Creation of Life Innovation Materials for Interdisciplinary Researcher Development (iLIM-1)

iLIM-O-4

Invited Lecture

Contacting thermoelectric CaCo- and CaMn-Ceramics with Cu wires
– From thermoelectric materials to modules–
Wilfried WUNDERLICH*
*
Tokai University, Fac. Eng., Material Science Department, Hiratsuka 259-1292, Japan
KEY WORDS: Energy Harvesting, Electro-Ceramics, Metal-Ceramic Interface, Microstructure

1. Introduction
The worldwide largest thermoelectric (TE) device
called “Yubatake” generates continuously 1 MW electric
power at the hot spring in Kusatsu-Onsen for more than 15
years without any significant maintenance [1]. Many
thermoelectric generators (TEG) use conventional TE
modules in the size of a few cm for independent energy
sources or utilizing the Peltier effect in air conditioners or
refrigerators. Up-scaling of ceramic-based TE’s can
increase the range of applications. New development has
increased the figure-of-merit ZT for the p- and n-type
thermoelectric materials Ca-Co-O (CCO) [2] ZT=0.4 and
Ca-Mn-O (CMO) [3] ZT=0.2 and produce a module [4] for
many new applications. Innovative impact came from the
recent discovery on cementious materials such as electric
conducting [5], self-cleaning [6], or self-sensing [7]
properties. We found that CMO and CCO are easy to
process self-compacting electro ceramics with good electric
conductivity. Using these materials, the aim is to increase
the performance of the overall module is the most important
issue for application as energy generator from waste heat.
We explain our experience with this system in the
following.
2. Experimental
2.1 Transport properties
After mixing and grinding the raw materials CaCO3
and Mn2O3 or a mixture of CoO with Co3O4, in the
following referred to as Co2O3, the cold pressed pellets
were calcined at 1000 oC for 7 h. The material was grinded,
pressed again and dried at room temperature. The Seebeck
voltage was measured under large temperature gradient and
the electric output power measured, as described before [8].
The dependence of the Seebeck coefficient S and the
electric output power ist shown in fig, 1 as a function of the
molar concentration CaO + Mn2O3 or Co2O3. For both
compounds the concentration range for best output
performance in between 28 to 33 mol%. In this range the
Seebeck coefficient is almost constant, but electric
conductivity is increasing and having the same ZT=0.4 and
0.2 for CCO and CMO as in [2,3].
The home-made device for measuring the Seebeck
coefficient has the advantage that we could change the
moisture during the measurement at high temperature. We
found that an increase in humidity decreases the Seebeck
coefficient drastically. The reason for this phenomenon is
known in literature as intercalation. The distance between
the co-conducting layers in materials such as NaCo2O3-x
and the high-temperature superconductor YBa2Cu3O7-x
increases in the presence of hydrogen.

2.2 Building a p-/n-Module
For building a module there are three different
geometries possible, as shown in fig 2. We can use a)
sintered powder, (b) wires or (c) sheets of Cu in order to
contact the electro-ceramics. In preliminary experiments,
we have produced all three compounds using Portland
cement instead of the ceramics. The result was good
electric conductivity depending on the Cu content for all
three cases, but bad mechanical stability for case (c). The
explanation is, the larger dimension the metal component
has, the larger are the mechanical stresses on the
metal-ceramic interface, which yield to mechanical failure
after a few loading cycles. The conclusion from these
experiemnts is that the wire geometry is the best.
The next experiment had the aim to check the
thermodynamic stability of the Cu-cement compound. The
SEM-EDX characterization in fig. 3 shows that Cu forms a
connecting network around the C3S, C2S C3A and CF
particles. In order to simulate long-time diffusion this
compound was also annealed in air for 7 h at 1100oC. No
decomposition was found (fig. 4 a) and the electric
conductivity remained high. Also other electric conducting
materials such as carbon fibers (fig. 4 b) and Ni were found
to be stable, while Fe was not.
The next check was to check the stability of CCO and
CMO. Calcined powder was mixed to wet cement paste.
The compound hardens, but as a result, it was found that

Fig. 1 (a,b) Seebeck Coefficient S and (c,d) electric output
power P at ΔT=550oC for (a,c) CaO-Mn2O3 and
(b,d) CaO-Co2O3 composite ceramics.

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Contacting thermoelectric CaCo- and CaMn-Ceramics with Cu wires

even the smallest tested volume fraction of 2 wt-% cement
decreases the electric conductivity drastically, so that the
output power vanishes, while the Seebeck coefficient
remains nearly unchanged. Similar results were found when
powder of refractories are added to CCO and CMO.
However, when CCO and CMO-slurry were pasted on
hardened cement did not affect the transport properties after
drying. Hence, we started the fabrication of the
thermoelectric module as shown in fig. 5. Cu-wires were
placed on grinded and shaped refractories and fixed with
cement paste. Then CCO and CMO-slurry were pasted
thereon in the usual n-p-geometry, where the p-n
connection is on the hot side, while the n-p connections are
on the cold side. After complete drying the module was
tested by placing on a heater. Although there are more
difficulties than expected this modules works.

Fig. 2 Geometry of metallic contact to ceramics.

4. Discussion
We need to explaining the fact, why the metallic
interconnections between CCO and CMO with Cu and Ni
are stable, while on the other hand Cement and any Si
decreases their transport properties. For the progress of a
chemical reaction we can get the data of the formation
energy from pure elements in a database [10]. Other checks
are energy per atom in calculated phase diagrams [10] and
the reaction of their components, which should be
consistent. We found, however, the fastest method is to
check the quaternary phase diagrams Ca-Mn-O-X and
Ca-Si-O-X with X = Si, Cu, Fe. Only in the Ca-Mn-Si-O
diagram there is a quaternary compound, in this case
CaMn4(SiO3)5, with has a not-vanishing “energy above
hull” (fig. 6) [10]. This explains why a small amount of Si
decomposes the CMO and CCO phases, while the metals
Cu, Fe, Ni and Zn are not harmful. This method can also
predict the stability of metallic contacts versus the
oxidation in these composite devices.

Fig. 3 SEM-EDX of Cu-Portland cement-composite.

Fig. 4 Portland cement with (a) Cu, (b) carbon fibers

5. Conculsion
The production of thermoelectric modules consisting of
CaCo- and CaMn-oxide electro-ceramics connected with
Cu-wires is possible and can have a large contribution for
energy generation from waste heat. A simple method for
check of thermodynamic phase stability is provided.

.
Fig 5 Preparation of Cu-wires for thermoelectric modules.

References
[1] T. Kajikawa, Journal Thermoelectricity 1 (2009) 18-27
[2] R. Funahashi, S. Urata, J. Mater. Res. 18 [7] (2003)
[3] Y.Wang, Y. Sui, W. Su, J. Appl. Phys. 104 (2008)
093703
[4] W. Liu, et al., Acta Mat. 87 (2015)357-376
[5] D.L.Chung, Adv. Cem. Res. 16 [4] (2004)167-176
[6] A. Zhao, et al. Cem. Con. Comp. 64 (2015) 74-83
[7] B. Han, S.Ding, X.Xu, Measurement 59 (2015)
110–128
[8] W. Wunderlich, Energy Harvest.Syst. 2 (2015) 37-46
[9] W. Wunderlich, Metals Mdpi 4 (2014) 410-427;
[10] Information on https://www.materialsproject.org
Fig 6 Phase diagram quaternary system Ca-Mn-Si-O.
.

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