Paper Thermoelectrics by a Solvent-Free Drawing Method of All Carbon-Based Materials.

As practical interest in the flexible or wearable thermoelectric generators (TEGs) has increased, the demand for the high-performance TEGs based on ecofriendly, mechanically resilient, and economically viable TEGs as alternatives to the brittle inorganic materials is growing. Organic or hybrid thermoelectric (TE) materials have been employed in flexible TEGs; however, their fabrication is normally carried out using wet processing such as spin-coating or screen printing. These techniques require materials dissolved or dispersed in solvents; thus, they limit the substrate choice. Herein, we have rationally designed solvent-free, all carbon-based TEGs dry-drawn on a regular office paper using few-layered graphene (FLG). This technique showed very good TE parameters, yielding a power factor of 97 µW m-1 K-2 at low temperatures. The p-type only device exhibited an output power of up to ∼19.48 nW. As a proof of concept, all carbon-based p-n TEGs were created on paper with the addition of HB pencil traces. The HB pencil exhibited low Seebeck coefficients (-7 µV K-1), and the traces were highly resistive compared to FLG traces, which resulted in significantly lower output power compared to the p-type only TEG. The demonstration of all carbon-based TEGs drawn on paper highlights the potential for future low-cost, flexible, and almost instantaneously created TEGs for low-power applications.

Full Thermoelectric Characterization of Stoichiometric Electrodeposited Thin Film Tin Selenide (SnSe).

Tin selenide (SnSe) has attracted much attention in the thermoelectric community since the discovery of the record figure of merit (ZT) of 2.6 in single crystal tin selenide in 2014. There have been many reports since of the thermoelectric characterization of SnSe synthesized or manufactured by several methods, but so far none of these have concerned the electrodeposition of SnSe. In this work, stoichiometric SnSe was successfully electrodeposited at -0.50 V vs SCE as shown by EDX, XPS, UPS, and XRD. The full ZT of the electrodeposits were then measured. This was done by both a delamination technique to measure the Seebeck coefficient and electrical conductivity which showed a peak power factor of 4.2 and 5.8 µW m-1 K-2 for the as deposited and heat-treated films, respectively. A novel modified transient 3ω method was used to measure the thermal conductivity of the deposited films on the deposition substrate. This revealed the thermal conductivity to be similar to the ultralow thermal conductivity of single crystal SnSe, with a value of 0.34 W m-1 K-1 being observed at 313 K.

Lightweight and Bulk Organic Thermoelectric Generators Employing Novel P-Type Few-Layered Graphene Nanoflakes.

Graphene exhibits both high electrical conductivity and large elastic modulus, which makes it an ideal material candidate for many electronic devices. At present not much work has been conducted on using graphene to construct thermoelectric devices, particularly due to its high thermal conductivity and lack of bulk fabrication. Films of graphene-based materials, however, and their nanocomposites have been shown to be promising candidates for thermoelectric energy generation. Exploring methods to enhance the thermoelectric performance of graphene and produce bulk samples can significantly widen its application in thermoelectrics. Realization of bulk organic materials in the thermoelectric community is highly desired to develop cheap, Earth-abundant, light, and nontoxic thermoelectric generators. In this context, this work reports a new approach using pressed pellets bars of few-layered graphene (FLG) nanoflakes employed in thermoelectric generators (TEGs). First, FLG nanoflakes were produced by a novel dry physical grinding technique followed by graphene nanoflake liberation using plasma treatment. The resultant material is highly pure with very low defects, possessing 3 to 5-layer stacks as proved by Raman spectroscopy, X-ray diffraction measurement, and scanning electron microscopy. The thermal and electronic properties confirm the anisotropy of the material and hence the varied performance characteristics parallel to and perpendicular to the pressing direction of the pellets. The full thermoelectric properties were characterized both parallel and perpendicular to the pressing direction, and the proof-of-concept thermoelectric generators were fabricated with variable amounts of legs.

Enhanced Electrical Conductivity and Seebeck Coefficient in PEDOT:PSS via a Two-Step Ionic liquid and NaBH4 Treatment for Organic Thermoelectrics.

A two-step approach of improving the thermoelectric properties of Poly(3,4-ethylenedioxythiophene)poly(4-styrenesulfonate) (PEDOT:PSS) via the addition of the ionic liquid, 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM:TFSI) and subsequent reduction with NaBH4 is presented. The addition of 2.5 v/v% of EMIM:TFSI to PEDOT:PSS increases the electrical conductivity from 3 S·cm-1 to 1439 S·cm-1 at 40 °C. An additional post treatment using the reducing agent, NaBH4, increases the Seebeck coefficient of the film from 11 µV·K-1 to 30 µV·K-1 at 40 °C. The combined treatment gives an overall improvement in power factor increase from 0.04 µW·m-1·K-2 to 33 µW·m-1·K-2 below 140 °C. Raman and XPS measurements show that the increase in PEDOT:PSS conductivity is due to PSS separation from PEDOT and a conformational change of the PEDOT chains from the benzoid to quinoid molecular orientation. The improved Seebeck coefficient is due to a reduction of charge carriers which is evidenced from the UV-VIS depicting the emergence of polarons.

Thin Film Tin Selenide (SnSe) Thermoelectric Generators Exhibiting Ultralow Thermal Conductivity.

Tin selenide (SnSe) has attracted much attention in the field of thermoelectrics since the discovery of the record figure of merit (ZT) of 2.6 ± 0.3 along the b-axis of the material. The record ZT is attributed to an ultralow thermal conductivity that arises from anharmonicity in bonding. While it is known that nanostructuring offers the prospect of enhanced thermoelectric performance, there have been minimal studies in the literature to date of the thermoelectric performance of thin films of SnSe. In this work, preferentially orientated porous networks of thin film SnSe nanosheets are fabricated using a simple thermal evaporation method, which exhibits an unprecedentedly low thermal conductivity of 0.08 W m-1 K-1 between 375 and 450 K. In addition, the first known example of a working SnSe thermoelectric generator is presented and characterized.