Mario Culebras

Review on Polymers for Thermoelectric Applications

In this review, we report the state-of-the-art of polymers in thermoelectricity. Classically, a number of inorganic compounds have been considered as the best thermoelectric materials. Since the prediction of the improvement of the figure of merit by means of electronic confinement in 1993, it has been improved by a factor of 3–4. In the mean time, organic materials, in particular intrinsically conducting polymers, had been considered as competitors of classical thermoelectrics, since their figure of merit has been improved several orders of magnitude in the last few years. We review here the evolution of the figure of merit or the power factor during the last years, and the best candidates to compete with inorganic materials. We also outline the best polymers to substitute classical thermoelectric materials and the advantages they present in comparison with inorganic systems.

Enhanced thermoelectric performance of PEDOT with different counter-ions optimized by chemical reduction

This work reports on the synthesis of the intrinsically conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) doped with several counter-ions, ClO4, PF6 and bis(trifluoromethylsulfonyl)imide (BTFMSI), by electro-polymerization and its thermoelectric properties. We show that, depending on the counter-ion size, the thermoelectric efficiency of PEDOT can be increased up to two orders of magnitude. A further chemical reduction with hydrazine optimizes the power factor (PF). By changing the counter-ions, we were able to increase the electrical conductivity (σ) of PEDOT by a factor of three, while the Seebeck coefficient remains at the same order of magnitude in the three polymers. The best thermoelectric efficiency has been observed in PEDOT:BTFMSI. From the measurement of the Seebeck coefficient and σ, a PF of 147 μW m−1 K−2 has been deduced, while the measured thermal conductivity is κ = 0.19 W m−1 K−1, resulting in a ZT ∼ 0.22 at room temperature, one of the highest values reported in the literature for polymers. The increase in σ with the change of the counter-ion is mainly due to the stretching of the polymer chains. In this work, we provide a chemical route to further improve ZT in polymers and demonstrate a method of synthesis based on the electro-polymerization on gold. After removing the gold layer, a very thin semiconducting polymer film can be isolated.

Optimization of Cell Growth on Bacterial Cellulose by Adsorption of Collagen and Poly-L-Lysine

Poly-L-lysine and collagen were separately added to bacterial cellulose (BC) nanofibers. The ionic surface charge had been previously modified in order to promote the adsorption of poly-L-lysine and collagen. Cell adhesion of Chinese hamster ovary (CHO) cells on BC surfaces was confirmed by removing unattached cells from the BC substrates. Cell viability was calculated and it was determined that both poly-L-lysine-BC and collagen-BC substrates are viable for cell growth. The results showed that the cell viability in poly-L-lysine modified BC substrate is similar to the one observed in polystyrene tissue culture plates. GRAPHICAL ABSTRACT

High Thermoelectric Power Factor Organic Thin Films through Combination of Nanotube Multilayer Assembly and Electrochemical Polymerization

In an effort to produce effective thermoelectric nanocomposites with multiwalled carbon nanotubes (MWCNT), layer-by-layer assembly was combined with electrochemical polymerization to create synergy that would produce a high power factor. Nanolayers of MWCNT stabilized with poly(diallyldimethylammonium chloride) or sodium deoxycholate were alternately deposited from water. Poly(3,4-ethylene dioxythiophene) [PEDOT] was then synthesized electrochemically by using this MWCNT-based multilayer thin film as the working electrode. Microscopic images show a homogeneous distribution of PEDOT around the MWCNT. The electrical resistance, conductivity (σ) and Seebeck coefficient (S) were measured before and after the PEDOT polymerization. A 30 bilayer MWCNT film (<1 μm thick) infused with PEDOT is shown to achieve a power factor (PF = S2σ) of 155 μW/m K2, which is the highest value ever reported for a completely organic MWCNT-based material and competitive with lead telluride at room temperature. The ability of this MWCNT-PEDOT film to generate power was demonstrated with a cylindrical thermoelectric generator that produced 5.5 μW with a 30 K temperature differential. This unique nanocomposite, prepared from water with relatively inexpensive ingredients, should open up new opportunities to recycle waste heat in portable/wearable electronics and other applications where low weight and mechanical flexibility are needed.

Monitoring molecular dynamics of bacterial cellulose composites reinforced with graphene oxide by carboxymethyl cellulose addition

Broadband Dielectric Relaxation Spectroscopy was performed to study the molecular dynamics of dried Bacterial Cellulose/Carboxymethyl Cellulose-Graphene Oxide (BC/CMC-GO) composites as a function of the concentration of CMC in the culture media. At low temperature the dielectric spectra are dominated by a dipolar process labelled as a β-relaxation, whereas electrode polarization and the contribution of dc-conductivity dominate the spectra at high temperatures and low frequency. The CMC concentration affects the morphological structure of cellulose and subsequently alters its physical properties. X-ray diffractometry measurements show that increasing the concentration of CMC promotes a decrease of the Iα/Iβ ratio. This structural change in BC, that involves a variation in inter- and intramolecular interactions (hydrogen-bonding interactions), affects steeply their molecular dynamics. So, an increase of CMC concentration produces a significantly decrease of the β-relaxation strength and an increase of the dc-conductivity.

La 1-x Ca x MnO 3 semiconducting nanostructures: morphology and thermoelectric properties.

Semiconducting metallic oxides, especially perosvkite materials, are great candidates for thermoelectric applications due to several advantages over traditionally metallic alloys such as low production costs and high chemical stability at high temperatures. Nanostructuration can be the key to develop highly efficient thermoelectric materials. In this work, La 1−xCaxMnO3 perosvkite nanostructures with Ca as a dopant have been synthesized by the hydrothermal method to be used in thermoelectric applications at room temperature. Several heat treatments have been made in all samples, leading to a change in their morphology and thermoelectric properties. The best thermoelectric efficiency has been obtained for a Ca content of x=0.5. The electrical conductivity and Seebeck coefficient are strongly related to the calcium content.

Confident methods for the evaluation of the hydrogen content in nanoporous carbon microfibers

Nanoporous carbon microfibers were grown by chemical vapor deposition in the vapor-liquid solid mode using different fluid hydrocarbons as precursors in different proportions. The as-grown samples were further treated in argon and hydrogen atmospheres at different pressure conditions and annealed at several temperatures in order to deduce the best conditions for the incorporation and re-incorporation of hydrogen into the microfibers through the nanopores. Since there are some discrepancies in the results on the hydrogen content obtained under vacuum conditions, in this work, we have measured the hydrogen content in the microfibers using several analytical methods in ambient conditions: surface tension, mass density, and Raman measurements. A discussion on the validity of the results obtained through the correlation between them is the purpose of the present work.

Manufacturing Te/PEDOT Films for Thermoelectric Applications

In this work, flexible Te films have been synthesized by electrochemical deposition using PEDOT [poly(3,4-ethylenedioxythiophene)] nanofilms as working electrodes. The Te electrodeposition time was varied to find the best thermoelectric properties of the Te/PEDOT double layers. To show the high quality of the Te films grown on PEDOT, the samples were analyzed by Raman spectroscopy, showing the three Raman active modes of Te: E1, A1, and E2. The X-ray diffraction spectra also confirmed the presence of crystalline Te on top of the PEDOT films. The morphology of the Te/PEDOT films was studied using scanning electron microscopy, showing a homogeneous distribution of Te along the film. Also an atomic force microscope was used to analyze the quality of the Te surface. Finally, the electrical conductivity and the Seebeck coefficient of the Te/PEDOT films were measured as a function of the Te deposition time. The films showed an excellent thermoelectric behavior, giving a maximum power factor of about 320 ± 16 μW m-1 K-2 after 2.5 h of Te electrochemical deposition, a value larger than that reported for thin films of Te. Qualitative arguments to explain this behavior are given in the discussion.

Changes in the thermoelectric response of vitreous carbon due to the irradiation by γ-rays

In order to study variations in the thermoelectric properties, some commercial glassy carbon samples were subjected to a sequence of steps consisting of a combination of irradiation with γ-rays produced by radioisotopes 60Co, and hydrogen adsorption when the samples were put in an over pressured atmosphere of this gas. With this procedure it was possible to observe that the irradiation decreases the electrical conductivity of glassy carbon samples and the hydrogenation changes the sign of Seebeck coefficient. The material initially is an n-type semiconductor, but with hydrogenation changes to p-type semiconductor. X-ray diffraction analysis showed that the hydrogenated vitreous carbon is more amorphous than the pristine material and the γ-rays irradiation produces changes in the crystallite size and shape.

Understanding the thermal and dielectric response of organosolv and modified kraft lignin as a carbon fibre precursor

Understanding the thermal behaviour of lignin is crucial in order to realise its valorisation as an engineering polymer. Two hardwood lignins, organosolv (OSL) and chemically modified kraft lignin (ML) have been chosen to represent important classes of renewable and abundant raw materials. The relationship between ionic mobility and viscosity in OSL and ML has been studied. The rheological results have been interpreted in terms of the competitive processes of thermal plasticisation and stiffening through crosslinking. Results show that with OSL, crosslinking proceeds relatively rapidly, and this is consistent with its more reactive structure. Higher molecular weight (Mw) influenced the melt stability as cross-linking kinetics was reduced and this was attributed to the reduction of chain ends available for cross-linking reactions. Scanning calorimetry has shown that both materials are glassy and pass through the glass transition between 100 °C and 115 °C, with the higher molecular weight modified material having a slightly higher Tg. Both lignins show pronounced maxima in the Gram–Schmidt plots for methane or methanol around 400 °C. However, a significant difference between the materials is observed with the detection of a strong carbonyl peak in the evolution products of the ML, which is attributed to the scission of the hydroxypropyl substituent present in the ML structure. The differences in the degradation processes are further reflected in the dielectric properties of the partially degraded materials where loss maxima occur at different temperatures and show different degrees of frequency dependence. An important observation is the difference in conductivity, where higher values for OSL are attributed to the cross-linking between adjacent benzene rings, whereas with the ML, a lower conductivity is associated with intrinsically less conductive intermolecular linkages. These results demonstrate that the thermal decomposition of the two lignins follows significantly different paths at the molecular level. With the more reactive OSL, it appears to be the case that there is a greater tendency to form direct ring to ring crosslinks and this is very significant for the properties of the intended end product.