Three-Dimensional Graphene Sheet-Carbon Veil Thermoelectric Composite with Microinterfaces for Energy Applications.

Over the years, various processing techniques have been explored to synthesize three-dimensional graphene (3DG) composites with tunable properties for advanced applications. In this work, we have demonstrated a new procedure to join a 3D graphene sheet (3DGS) synthesized by chemical vapor deposition (CVD) with a commercially available carbon veil (CV) via cold rolling to create 3DGS-CV composites. Characterization techniques such as scanning electron microscopy (SEM), Raman mapping, X-ray diffraction (XRD), electrical resistance, tensile strength, and Seebeck coefficient measurements were performed to understand various properties of the 3DGS-CV composite. Extrusion of 3DGS into the pores of CV with multiple microinterfaces between 3DGS and the graphitic fibers of CV was observed, which was facilitated by cold rolling. The extruded 3D graphene revealed pristine-like behavior with no change in the shape of the Raman 2D peak and Seebeck coefficient. Thermoelectric (TE) power generation and photothermoelectric responses have been demonstrated with in-plane TE devices of various designs made of p-type 3DGS and n-type CV couples yielding a Seebeck coefficient of 32.5 µV K-1. Unlike various TE materials, 3DGS, CV, and the 3DGS-CV composite were very stable at high relative humidity. The 3DGS-CV composite revealed a thin, flexible profile, good moisture and thermal stability, and scalability for fabrication. These qualities allowed it to be successfully tested for temperature monitoring of a Li-ion battery during charging cycles and for large-area temperature mapping.

Manufacturing Scalable Carbon Nanotube-Silicone/Kevlar Fabrics.

Carbon nanotube (CNT) hybrid composites were formed by combining a CNT and silicone elastomer solution with Kevlar yarn, Kevlar fabric, and Kevlar veil materials. The integration of a CNT-silicone matrix with Kevlar yarn and fabric materials produced a composite with moderate electrical and thermal conductivity due to CNT fabric combined with the strength of Kevlar fabric or yarn. In the material synthesis, a notable difficulty was that the CNT-silicone did not bond strongly to the Kevlar. The composites passed the Vertical Flame Test ASTM D6413 and the Forced Air Oven Test NFPA 1971. These hybrid composites can have multiple applications in areas requiring favorable conductivity, strength, and flame and heat resistance. The application areas include firefighter apparel, military equipment, conductive/smart structures, and flexible electronics. The synthesis process used to manufacture CNT-silicone/Kevlar composites yielded composite sheets with an area of 2250 cm2. The process is scalable and customizable for the synthesis of CNT composites with tailored properties. Improvements in the bonding of CNT-silicone to Kevlar are being investigated.

Boosting Thermoelectric Power Factor of Carbon Nanotube Networks with Excluded Volume by Co-Embedded Microparticles.

Carbon nanotube (CNT) networks embedded in a polymer matrix have been extensively studied as a flexible thermoelectric transport medium over the recent years. However, their power factor has been largely limited by the relatively inefficient tunneling transport at junctions between CNTs and the low-density conducting channels throughout the networks. This work demonstrates that significant power factor enhancements can be achieved by adding electrically insulating microscale particles in three-dimensional CNT networks embedded in the polymer matrix. When silica particles of a few µm diameters were co-embedded in single-walled CNT (SWCNT)-polydimethylsiloxane (PDMS) composites, both the electrical conductivity and the Seebeck coefficient were simultaneously enhanced, thereby boosting the power factor by more than a factor of six. We found that the silica microparticles excluded a large volume of the composite from the access of CNTs and caused CNT networks to form around them with the polymer as a binder, resulting in improved network connectivity and alignment of CNTs. Our theoretical calculations based on junction tunneling transport for three-dimensional CNT networks show that the significant power factor enhancement can be attributed to the enhanced tunneling with reduced junction distance between CNTs. Additional power factor enhancement by a factor of three was achieved by sample compression, which further reduced the mean junction distance to enhance tunneling but also reduced the geometric factor at the same time, limiting the enhancement of electrical conductivity.

CVD Synthesis of 3D-Shaped 3D Graphene Using a 3D-Printed Nickel-PLGA Catalyst Precursor.

Earlier, various attempts to develop graphene structures using chemical and nonchemical routes were reported. Being efficient, scalable, and repeatable, 3D printing of graphene-based polymer inks and aerogels seems attractive; however, the produced structures highly rely on a binder or an ice support to stay intact. The presence of a binder or graphene oxide hinders the translation of the excellent graphene properties to the 3D structure. In this communication, we report our efforts to synthesize a 3D-shaped 3D graphene (3D2G) with good quality, desirable shape, and structure control by combining 3D printing with the atmospheric pressure chemical vapor deposition (CVD) process. Direct ink writing has been used in this work as a 3D-printing technique to print nickel powder-PLGA slurry into various shapes. The latter has been employed as a catalyst for graphene growth via CVD. Porous 3D2G with high purity was obtained after etching out the nickel substrate. The conducted micro CT and 2D Raman study of pristine 3D2G revealed important features of this new material. The interconnected porous nature of the obtained 3D2G combined with its good electrical conductivity (about 17 S/cm) and promising electrochemical properties invites applications for energy storage electrodes, where fast electron transfer and intimate contact with the active material and with the electrolyte are critically important. By changing the printing design, one can manipulate the electrical, electrochemical, and mechanical properties, including the structural porosity, without any requirement for additional doping or chemical postprocessing. The obtained binder-free 3D2G showed a very good thermal stability, tested by thermo-gravimetric analysis in air up to 500 °C. This work brings together two advanced manufacturing approaches, CVD and 3D printing, thus enabling the synthesis of high-quality, binder-free 3D2G structures with a tailored design that appeared to be suitable for multiple applications.