Académique Documents
Professionnel Documents
Culture Documents
7-8
in conjunction with 1st Int. Symp. Creation of Life Innovation Materials for Interdisciplinary Researcher Development (iLIM-1)
iLIM-O-4
Invited Lecture
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 TEs 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.
- 7-
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.
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)
110128
[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.
.
- 8-