High-Hole-Mobility Fiber Organic Electrochemical Transistors for Next-Generation Adaptive Neuromorphic Bio-Hybrid Technologies.

The latest developments in fiber design and materials science are paving the way for fibers to evolve from parts in passive components to functional parts in active fabrics. Designing conformable, organic electrochemical transistor (OECT) structures using poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) fibers has excellent potential for low-cost wearable bioelectronics, bio-hybrid devices, and adaptive neuromorphic technologies. However, to achieve high-performance, stable devices from PEDOT:PSS fibers, approaches are required to form electrodes on fibers with small diameters and poor wettability, that leads to irregular coatings. Additionally, PEDOT:PSS-fiber fabrication needs to move away from small batch processing to roll-to-roll or continuous processing. Here, it is shown that synergistic effects from a superior electrode/organic interface, and exceptional fiber alignment from continuous processing, enable PEDOT:PSS fiber-OECTs with stable contacts, high µC* product (1570.5 F cm-1 V-1 s-1 ), and high hole mobility over 45 cm2 V-1 s-1 . Fiber-electrochemical neuromorphic organic devices (fiber-ENODes) are developed to demonstrate that the high mobility fibers are promising building blocks for future bio-hybrid technologies. The fiber-ENODes demonstrate synaptic weight update in response to dopamine, as well as a form factor closely matching the neuronal axon terminal.

Utilization of Lignin-Derived Small Molecules: Epoxy Polymers from Lignin Oxidation Products.

Much effort has been invested in developing methods for producing small molecules from lignin as a way to source feedstock chemicals from renewable sources. Significant progress is being made, and methods for deconstructing lignin are producing good yields of small, mononuclear aromatic products-sufficient amounts to enable studies of the potential use of these compounds as replacements for compounds currently produced from petroleum. To investigate the use of lignin products in epoxies, we begin with aromatic acids that can be produced from lignin, treat them with epichlorohydrin to make glycidyl ethers, and investigate the thermal and mechanical properties of cured mixtures of these compounds with a commercial epoxy resin (EPON 826) and an anhydride curing agent (NMA). While most of the lignin-modified epoxy polymers exhibit good physical and thermal properties, the polymer prepared from p-hydroxybenzoic acid (compound 6) has a higher glass-transition temperature (Tg = 159 °C) than do thermosets made with other lignin-derived materials, such as vanillic acid diglycidyl ether (compound 4) and matches the Tg of cured samples of the commercial EPON-826/NMA epoxy system. This is significant, as p-hydroxybenzoic acid is readily available by simple hydrolysis of several different lignins and functions as a drop-in replacement for 50% of the BPA-based material in this commercial system without significant degradation of material properties. The use of lignin-derived small molecules in high-value systems such as epoxies may help improve the economics of biorefineries.

Tailoring the Seebeck Coefficient of Spray-Coated Poly(3,4-ethylenedioxythiophene): Poly(styrenesulfonate) Films with Nitrogen Doped Multiwalled Carbon Nanotubes.

The thermoelectric properties of flexible thin films fabricated from two commercial poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) formulations filled with multiwalled carbon nanotubes (MWCNT) and nitrogen-doped MWCNT (N-MWCNT) were investigated. A simple spray-coating method for the fabrication of such flexible films on a polyethylene terephthalate substrate was developed. While increasing the MWCNT concentration had little effect on the thermoelectric properties, increasing the N-MWCNT concentration resulted in the emergence of an overall n-type semiconducting behavior and, thereby, tailoring the Seebeck coefficient of the composite films from p-type to n-type was shown. The Seebeck coefficient of the two PEDOT:PSS formulation films was inverted from 4.1 to -13.3 µV/K and from 12.5 to -10.9 µV/K respectively, with increasing N-MWCNT concentration from 0 to 95 wt.%. The importance of these results for future work stems from the possibility of tailoring the behavior of a typical p-type polymer such as PEDOT:PSS and the effect that the polymer conductive grade has on the switching concentration.

All-Organic Textile Thermoelectrics with Carbon-Nanotube-Coated n-Type Yarns.

Thermoelectric textiles that are able to generate electricity from heat gradients may find use as power sources for a wide range of miniature wearable electronics. To realize such thermoelectric textiles, both p- and n-type yarns are needed. The realization of air-stable and flexible n-type yarns, i.e., conducting yarns where electrons are the majority charge carriers, presents a considerable challenge due to the scarcity of air-stable n-doped organic materials. Here, we realize such n-type yarns by coating commercial sewing threads with a nanocomposite of multiwalled carbon nanotubes (MWNTs) and poly(N-vinylpyrrolidone) (PVP). Our n-type yarns have a bulk conductivity of 1 S cm-1 and a Seebeck coefficient of -14 µV K-1, which is stable for several months at ambient conditions. We combine our coated n-type yarns with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) dyed silk yarns, constituting the p-type component, to realize a textile thermoelectric module with 38 n/p elements, which are capable of producing an open-circuit voltage of 143 mV when exposed to a temperature gradient of 116 °C and a maximum power output of 7.1 nW at a temperature gradient of 80 °C.

Spray-Coated Multiwalled Carbon Nanotube Composite Electrodes for Thermal Energy Scavenging Electrochemical Cells.

Spray-coated multiwalled carbon nanotube/poly(vinylidene fluoride) (MWCNT/PVDF) composite electrodes, scCNTs, with varying CNT compositions (2 to 70 wt %) are presented for use in a simple thermal energy-scavenging cell (thermocell) based on the ferro/ferricyanide redox couple. Their utility for direct thermal-to-electrical energy conversion is explored at various temperature differentials and cell orientations. Performance is compared to that of buckypaper, a 100% CNT sheet material used as a benchmark electrode in thermocell research. The 30 to 70 wt % scCNT composites give the highest power output by electrode area-seven times greater than buckypaper at ΔT = 50 °C. CNT utilization is drastically enhanced in our electrodes, reaching 1 W gCNT(-1) compared to 0.036 W gCNT(-1) for buckypaper. Superior performance of our spray-coated electrodes is attributed to both wettability with better use of a large portion of electrochemically active CNTs and minimization of ohmic and thermal contact resistances. Even composites with as low as 2 wt % CNTs are still competitive with prior art. The MWCNT/PVDF composites developed herein are inexpensive, scalable, and serve a general need for CNT electrode optimization in next-generation devices.

Photoinduced p- to n-type Switching in Thermoelectric Polymer-Carbon Nanotube Composites.

UV-induced switching from p- to n-type character is demonstrated during deposition of carbon-nanotube-conjugated polymer composites. This opens the possibility to photopattern n-type regions within an otherwise p-type film, which has a potential for complementary circuitry or, as shown here, thermoelectric generators made from a single solution.

Continuous Processing of Multi-Walled Carbon Nanotube-Studded Carbon Fiber Tapes for Enhanced Through-Thickness Thermal Diffusivity Composites.

Carbon fiber reinforced polymer (CFRP) composites offer advantages over traditional metallic structures, particularly specific strength and stiffness, but at much reduced thermal conductivity. Moreover, fiber-to-fiber heat conduction in the composite transverse directions is significantly lower. When these structures contain electronics (heat generators), shortfalls in heat transport can be problematic. Here we report the achievement of a continuous, reel-to-reel process for growing short multiwalled carbon nanotubes (MWCNT) on the surfaces of spread-tow carbon fiber tapes. These tapes were subsequently prepregged with an epoxy matrix, and laid up into multi-ply laminate panels, cured and tested for through-thickness thermal diffusivity. The results showed up to a 57% increase in through thickness thermal diffusivity compared to the baseline composite with no MWCNT.