Recent Advances in Air-Stable n-Type Single-Walled Carbon Nanotube Composites for Thermoelectric Applications

With the rapid advancement of the IoT society and growing awareness of environmental issues, thermoelectric conversion technology—which directly converts waste heat into electricity—is gaining attention as a self-powered, autonomous power source capable of driving countless devices. While currently mainstream metal-based inorganic thermoelectric materials demonstrate high performance, their high rigidity and brittleness, as well as their frequent inclusion of toxic heavy metals, have limited their application in biological systems and on curved surfaces. As a next-generation alternative, single-walled carbon nanotubes (SWCNTs)—which possess excellent flexibility, electrical conductivity, and mechanical strength while being low in toxicity—are garnering significant attention. However, n-type SWCNT materials, which are essential for thermoelectric module fabrication, have faced two major barriers to practical application: low atmospheric stability (they easily revert to p-type upon exposure to atmospheric oxygen and moisture) and thermoelectric performance that falls short of inorganic materials. This review comprehensively outlines the latest composite approaches designed to overcome these critical challenges and achieve both extreme atmospheric stability and high thermoelectric performance in n-type SWCNT materials, along with the flexibility required to withstand severe deformation. Three main strategies are discussed. The first is the organic/polymer approach, which involves doping with organic small molecules that control the LUMO level or bicyclic organic superbases with strong electron-donating properties, as well as polymer coating, to achieve long-term stable n-type characteristics and high power output even in air or under severe high-temperature conditions. The second is the inorganic hybrid strategy, which involves nanoscale compositing with inorganic materials such as Bi2Te3 and Cu2O; this reduces thermal conductivity through phonon scattering via interface control, while the inorganic layer physically blocks oxygen to ensure long-term atmospheric stability. The third approach involves ultra-long-term stabilization techniques, such as bulk encapsulation using cationic or gemini surfactants, and environmentally friendly aqueous processes utilizing natural amino acids. Furthermore, we discuss the latest developments in imparting practical-level toughness (flexibility) capable of withstanding thousands of bending cycles and high tensile stress through the introduction of dynamic covalent network polymers and elastomers. The conformal flexible thermoelectric power generation modules created through the integration of composite optimization, low-environmental-impact processes, and doping techniques will serve as a crucial foundational technology for realizing a sustainable next-generation electronics society, including future wearable devices, artificial skin, and smart sensor networks.