SWNT Anchored with Carboxylated Polythiophene "Links" on High-Capacity Li-Ion Battery Anode Materials.

Conjugated polymers possessing polar functionalities were shown to effectively anchor single-walled carbon nanotubes (SWNTs) to the surface of high-capacity anode materials and enable the formation of electrical networks. Specifically, poly[3-(potassium-4-butanoate) thiophene] (PPBT) served as a bridge between SWNT networks and various anode materials, including monodispersed Fe3O4 spheres (sFe3O4) and silicon nanoparticles (Si NPs). The PPBT π-conjugated backbone and carboxylate (COO-) substituted alkyl side chains, respectively, attracted the SWNT π-electron surface and chemically interacted with active material surface hydroxyl (-OH) species to form a carboxylate bond. Beneficially, this architecture effectively captured cracked/pulverized particles that typically form as a result of repeated active material volume changes that occur during charging and discharging. Thus, changes in electrode thickness were suppressed substantially, stable SEI layers were formed, electrode resistance was reduced, and enhanced electrode kinetics was observed. Together, these factors led to excellent electrochemical performance.

Anisotropic Responsive Microgels Based on the Cholesteric Phase of Chitin Nanocrystals.

Anisotropic stimuli-responsive microgels based upon the cholesteric phase of chitin nanocrystals and N-isopropylacrylamide were designed and synthesized. The cholesteric structure was interrogated, and the texture was shown to directly influence the microgel shape and anisotropy. Changes in the microgel volume led to changes in the texture, where microgels comprising up to six bands exhibited a twisted bipolar texture, while those with greater volumes displayed a concentric-packing structure. As designed, the imprinted cholesteric phase induced an asymmetric response to temperature, leading to a change in shape and optical properties. Furthermore, the cholesteric structure is able to deform, facilitating transport into a small channel. Access to synthetic structures having a self-assembled twisted texture derived from cholesterics embedded within a polymer matrix will provide guidelines for designing biopolymer composites with programmable motion.

Carbon Nanotube Web with Carboxylated Polythiophene "Assist" for High-Performance Battery Electrodes.

A carbon nanotube (CNT) web electrode comprising magnetite spheres and few-walled carbon nanotubes (FWNTs) linked by the carboxylated conjugated polymer, poly[3-(potassium-4-butanoate) thiophene] (PPBT), was designed to demonstrate benefits derived from the rational consideration of electron/ion transport coupled with the surface chemistry of the electrode materials components. To maximize transport properties, the approach introduces monodispersed spherical Fe3O4 (sFe3O4) for uniform Li+ diffusion and a FWNT web electrode frame that affords characteristics of long-ranged electronic pathways and porous networks. The sFe3O4 particles were used as a model high-capacity energy active material, owing to their well-defined chemistry with surface hydroxyl (-OH) functionalities that provide for facile detection of molecular interactions. PPBT, having a π-conjugated backbone and alkyl side chains substituted with carboxylate moieties, interacted with the FWNT π-electron-rich and hydroxylated sFe3O4 surfaces, which enabled the formation of effective electrical bridges between the respective components, contributing to efficient electron transport and electrode stability. To further induce interactions between PPBT and the metal hydroxide surface, polyethylene glycol was coated onto the sFe3O4 particles, allowing for facile materials dispersion and connectivity. Additionally, the introduction of carbon particles into the web electrode minimized sFe3O4 aggregation and afforded more porous FWNT networks. As a consequence, the design of composite electrodes with rigorous consideration of specific molecular interactions induced by the surface chemistries favorably influenced electrochemical kinetics and electrode resistance, which afforded high-performance electrodes for battery applications.