Choongho Yu

Measuring Thermal and Thermoelectric Properties of One-Dimensional Nanostructures Using a Microfabricated Device

We have batch-fabricated a microdevice consisting of two adjacent symmetric silicon nitride membranes suspended by long silicon nitride beams for measuring thermophysical properties of one-dimensional manostructures (nanotubes, nanowires, and mmobelts) bridging the two membranes. A platinum resistance heater/thermometer is fabricated on each membrane. One membrane can be Joule heated to cause heat conduction through the sample to the other membrane. Thermal conductance, electrical conductance, and Seebeck coefficient can be measured using this microdevice in the temperature range of 4-400 K of an evacuated Helium cryostat. Measurement sensitivity, errors, and uncertainty are discussed. Measurement results of a 148 nm and a 10 nm-diameter single wall carbon nanotube bundle are presented.

Improved Thermoelectric Behavior of Nanotube-Filled Polymer Composites with Poly(3,4-ethylenedioxythiophene) Poly(styrenesulfonate)

The thermoelectric properties of carbon nanotube (CNT)-filled polymer composites can be enhanced by modifying junctions between CNTs using poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), yielding high electrical conductivities (up to approximately 40000 S/m) without significantly altering thermopower (or Seebeck coefficient). This is because PEDOT:PSS particles are decorated on the surface of CNTs, electrically connecting junctions between CNTs. On the other hand, thermal transport remains comparable to typical polymeric materials due to the dissimilar bonding and vibrational spectra between CNT and PEDOT:PSS. This behavior is very different from that of typical semiconductors whose thermoelectric properties are strongly correlated. The decoupled thermoelectric properties, which is ideal for developing better thermoelectric materials, are believed to be due to thermally disconnected and electrically connected contact junctions between CNTs. Carrier transport at the junction is found to be strongly dependent on the type and concentration of stabilizers. The crucial role of stabilizers was revealed by characterizing transport characteristics of composites synthesized by electrically conducting PEDOT:PSS and insulating gum Arabic (GA) with 1:1-1:4 weight ratios of CNT to stabilizers. The influence of composite synthesis temperature and CNT-type and concentration on thermoelectric properties has also been studied. Single-walled (SW) CNT-filled composites dried at room temperature followed by 80 degrees C exhibited the best thermoelectric performance in this study. The highest thermoelectric figure of merit (ZT) in this study is estimated to be approximately 0.02 at room temperature, which is at least one order of magnitude higher than most polymers and higher than that of bulk Si. Further studies with various polymers and nanoparticles with high thermoelectric performance may result in economical, lightweight, and efficient polymer thermoelectric materials.

Thermoelectric Behavior of Segregated-Network Polymer Nanocomposites

Segregated-network carbon nanotube (CNT)-polymer composites were prepared, and their thermoelectric properties were measured as a function of CNT concentration at room temperature. This study shows that electrical conductivity can be dramatically increased by creating a network of CNTs in the composite, while the thermal conductivity and thermopower remain relatively insensitive to the filler concentration. This behavior results from thermally disconnected, but electrically connected, junctions in the nanotube network, which makes it feasible to tune the properties in favor of a higher thermoelectric figure of merit. With a CNT concentration of 20 wt %, these composites exhibit an electrical conductivity of 4800 S/m, thermal conductivity of 0.34 W/m x K and a thermoelectric figure of merit (ZT) greater than 0.006 at room temperature. This study suggests that polymeric thermoelectrics are possible and provides the basis for further development of lightweight, low-cost, and nontoxic polymer composites for thermoelectric applications in the future.

Light-Weight Flexible Carbon Nanotube Based Organic Composites with Large Thermoelectric Power Factors

Typical organic materials have low thermal conductivities that are best suited to thermoelectrics, but their poor electrical properties with strong adverse correlations have prevented them from being feasible candidates. Our composites, containing single-wall carbon nanotubes, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) and/or polyvinyl acetate, show thermopowers weakly correlated with electrical conductivities, resulting in large thermoelectric power factors in the in-plane direction of the composites, ∼160 μW/m·K(2) at room temperature, which are orders of magnitude larger than those of typical polymer composites. Furthermore, their high electrical conductivities, ∼10(5) S/m at room temperature, make our composites very promising for various electronic applications. The optimum nanotube concentrations for better power factors were identified to be 60 wt % with 40 wt % polymers. It was noticed that high nanotube concentrations above 60 wt % decreased the electrical conductivity of the composites due to less effective nanotube dispersions. The thermal conductivities of our 60 wt % nanotube composites in the out-of-plane direction were measured to be 0.2-0.4 W/m·K at room temperature. The in-plane thermal conductivity and thermal contact conductance between nanotubes were also theoretically estimated.

Thermal Contact Resistance and Thermal Conductivity of a Carbon Nanofiber

It has been suggested that CNTs and carbon nanofibers CNFs can be used as thermal interface materials to enhance contact thermal conductance for electronic packaging applications. Several groups have reported mixed experimental results from no improvements to large improvements in the thermal contact conductance due to the CNTs and CNFs 8‐12. These mixed results can be caused by the difference in surface coverage and perpendicular alignment of the CNTs or CNFs. Moreover, the results can be affected by two other factors. First, the CNTs and CNFs grown using different methods possess different defect densities and different intrinsic thermal conductivities. Secondly, the contact thermal resistance of the nanometer scale point and line contacts between a CNT or CNF and a planar surface can be high due to enhanced phonon-boundary scattering at the nanocontacts. We have used a microfabricated device to measure the thermal resistance of an individual CNF from a vertically aligned CNF film for applications as thermal interface materials. The measurement was conducted before and after a platinum Pt layer was deposited on the contacts between the CNF and the microdevice so as to investigate the thermal contact resistance between the CNF and a planar surface. The contact resistance was reduced by the platinum coating for about 9‐13% of the total thermal resistance of the nanofiber sample before the Pt coating. At temperature 300 K, the obtained axial thermal conductivity of the carbon nanofibers was about three times smaller than that of graphite fibers grown by pyrolysis of natural gas prior to high-temperature heat treatment.

Completely Organic Multilayer Thin Film with Thermoelectric Power Factor Rivaling Inorganic Tellurides

Composed exclusively of organic components, polyaniline (PANi), graphene, and double-walled nanotubes (DWNTs) are alternately deposited from aqueous solutions using a layer-by-layer assembly. The 40 quadlayer thin film (470 nm thick) exhibits electrical conductivity of 1.08 × 10(5) S m(-1) and a Seebeck coefficient of 130 μV K(-1) , producing a thermoelectric power factor of 1825 μW m(-1) K(-2) .

Air-stable fabric thermoelectric modules made of N- and P-type carbon nanotubes

This report demonstrates an exciting new paradigm for thermoelectric energy conversion with both n- and p-type organic materials that possess mechanical flexibility, simple fabrication processes, and stability in air. In order to synthesize n-type samples with membranes and papers, carbon nanotubes were doped with both polyethyleneimine (PEI) and sodium borohydride (NaBH4), showing excellent n-type characteristics with thermopower values as large as −80 μV K−1. Thermoelectric modules made of both n- and p-type composites were fabricated to demonstrate thermoelectric voltage and power generation with one, two, and three p–n couples connected in series. The testing modules produced ∼6 mV thermoelectric voltage, with ∼25 nW generated power upon application of ∼22 °C temperature gradients. These promising results show that further work with many junctions connected in series would result in scalable organic p–n couple modules, which can generate power from temperature gradients or provide cooling for various electronic devices.

Flexible Power Fabrics Made of Carbon Nanotubes for Harvesting Thermoelectricity

Thermoelectric energy conversion is very effective in capturing low-grade waste heat to supply electricity particularly to small devices such as sensors, wireless communication units, and wearable electronics. Conventional thermoelectric materials, however, are often inadequately brittle, expensive, toxic, and heavy. We developed both p- and n-type fabric-like flexible lightweight materials by functionalizing the large surfaces and junctions in carbon nanotube (CNT) mats. The poor thermopower and only p-type characteristics of typical CNTs have been converted into both p- and n-type with high thermopower. The changes in the electronic band diagrams of the CNTs were experimentally investigated, elucidating the carrier type and relatively large thermopower values. With our optimized device design to maximally utilize temperature gradients, an electrochromic glucose sensor was successfully operated without batteries or external power supplies, demonstrating self-powering capability. While our fundamental study provides a method of tailoring electronic transport properties, our device-level integration shows the feasibility of harvesting electrical energy by attaching the device to even curved surfaces like human bodies.

Lossless hybridization between photovoltaic and thermoelectric devices

The optimal hybridization of photovoltaic (PV) and thermoelectric (TE) devices has long been considered ideal for the efficient harnessing solar energy. Our hybrid approach uses full spectrum solar energy via lossless coupling between PV and TE devices while collecting waste energy from thermalization and transmission losses from PV devices. Achieving lossless coupling makes the power output from the hybrid device equal to the sum of the maximum power outputs produced separately from individual PV and TE devices. TE devices need to have low internal resistances enough to convey photo-generated currents without sacrificing the PV fill factor. Concomitantly, a large number of p-n legs are preferred to drive a high Seebeck voltage in TE. Our simple method of attaching a TE device to a PV device has greatly improved the conversion efficiency and power output of the PV device (~30% at a 15°C temperature gradient across a TE device).

Scalable synthesis of bi-functional high-performance carbon nanotube sponge catalysts and electrodes with optimum C–N–Fe coordination for oxygen reduction reaction

Oxygen reduction reaction (ORR) is essential in various electrochemical energy conversion processes, but its sluggish kinetics calls for catalysts made of platinum or its alloys. Although their high catalytic activity has been hardly challenged, the high price of the precious metal has limited their wide applications. Nitrogen-doped carbonaceous materials have been reported as alternatives due to the low cost of carbon and nitrogen precursors, but the low-cost has accompanied by low catalytic activity and poor stability, particularly in acidic media. Here we developed 3-dimentional (3D) N/Fe-containing carbon nanotube (CNT) sponges showing striking improvements in catalytic activity and stability in both acidic and basic solutions. The onset potential and limiting current density in 0.5 M H2SO4 or 0.1 M KOH were comparable to those of Pt/C (20 wt% Pt). More importantly, cyclic voltammetry (CV) tests up to 30 000 cycles suggest their excellent long-term stability even better than those of Pt/C. We believe that the key for the high performance is pyridinic nitrogen coordinated with iron in 3D CNTs, according to the comparative studies with their variants whose characteristics include iron-deficiency as well as nitrogen doping with weak iron coordination. This study demonstrates that a proper doping, coordination, and morphology design of CNT bulks could lead to an outstanding performance, and the findings will be of great value for further improving non-precious metal catalysts. The self-standing and porous sponge-like 3D structure could substantially facilitate the mass transfer for ORR and, therefore, potentially act as a gas diffusion layer in electrochemical cells. The unique bi-functionality with a low cost but a high performance could make fuel cells as commercially viable options in the future.