Lack of high-performance cathode materials has become a technological bottleneck for the commercial development of advanced Li-ion batteries. We have proposed a biomimetic design and versatile synthesis of ultrathin spinel membrane-encapsulated layered lithium-rich cathode, a modification by nanocoating. The ultrathin spinel membrane is attributed to the superior high reversible capacity (over 290 mAh g(-1)), outstanding rate capability, and excellent cycling ability of this cathode, and even the stubborn illnesses of the layered lithium-rich cathode, such as voltage decay and thermal instability, are found to be relieved as well. This cathode is feasible to construct high-energy and high-power Li-ion batteries.

Covalent doping of single-walled carbon nanotubes (SWCNTs) can modify their optical properties, enabling applications as single-photon emitters and bio-imaging agents. We report here a simple, quick, and controllable method for preparing oxygen-doped SWCNTs with desirable emission spectra. Aqueous nanotube dispersions are treated at room temperature with NaClO (bleach) and then UV-irradiated for less than one minute to achieve optimized O-doping. The doping efficiency is controlled by varying surfactant concentration and type, NaClO concentration, and irradiation dose. Photochemical action spectra indicate that doping involves reaction of SWCNT sidewalls with oxygen atoms formed by photolysis of ClO − ions. Variance spectroscopy of products reveals that most individual nanotubes in optimally treated samples show both pristine and doped emission. A continuous flow reactor is described that allows efficient preparation of milligram quantities of O-doped SWCNTs. Finally, we demonstrate a bio-imaging application that gives high contrast short-wavelength infrared fluorescence images of vasculature and lymphatic structures in mice injected with only ~100 ng of the doped nanotubes.

Each structural form of single-wall carbon nanotube (SWCNT) has remarkable and well-defined electronic and optical properties, but it has not been possible to achieve spatial or energetic modulation of those properties in controllable ways. We present here a simple method for using chemical reactions with single-stranded DNA (ssDNA) to accomplish such modulation. When aqueous suspensions of SWCNTs coated with ssDNA are exposed to singlet oxygen under ambient conditions, the nanotubes selectively form covalent bonds to the guanine nucleotides. This locally modulates semiconducting SWCNT energy levels and red-shifts their emission wavelengths by up to 10%. Both the magnitude and spatial pattern of these shifts can be controlled by selecting the nucleotide sequence used to coat the nanotubes. Biomedical and optoelectronic applications are foreseen.

Covalent functionalization of single-wall carbon nanotubes (SWCNTs) can be valuable for modifying their electronic properties and creating fluorescent quantum defects. We report here a previously unreported category of such reactions involving interactions of photoexcited aromatic compounds with SWCNT sidewalls. When aqueous suspensions of SWCNTs are exposed to organic aromatic compounds and then irradiated by UV light, fluorescent defects are formed in the nanotubes at rates that depend on the aromatic ring substituents. In reactions with aniline or iodoaniline, strong spectral sidebands appear within 1 min. Total SWCNT photoluminescence can be enhanced by a factor as large as ∼5. Notably, emission spectra of reacted SWCNTs depend on the presence or absence of dissolved oxygen during the reaction. For (6,5) SWCNTs, treatment when oxygen is present gives an additional emission band red-shifted by 160 meV from the pristine position, whereas treatment without oxygen leads to two additional emission bands red-shifted by 140 and 270 meV. Variance spectroscopy shows the presence of individual “multicolor” nanotubes with three distinct emission bands (pristine plus two shifted). The facile generation of dual fluorescent quantum defects in SWCNTs provides emission closer to standard telecom wavelengths, advancing the prospects for applications as single-photon sources in quantum information processing.

Chemical reactions between semiconducting single-wall carbon nanotubes (SWCNTs) and single-stranded DNA (ssDNA) achieve spatially patterned covalent functionalization sites and create coupled fluorescent quantum defects on the nanotube surface, tailoring SWCNT photophysics for applications such as single-photon emitters in quantum information technologies. The evaluation of relaxation dynamics of photoluminescence (PL) from those coupled quantum defects is essential for understanding the nanotube electronic structure and beneficial to the design of quantum light emitters. Here, we measured the PL decay for ssDNA-functionalized SWCNTs as a function of the guanine content of the ssDNA oligo that dictates the red-shifting of their PL emission peaks relative to the band-edge exciton. We then correlate the observed dependence of PL decay dynamics on energy red-shifts to the exciton potential energy landscape, which is modeled using first-principles approaches based upon the morphology of ssDNA-altered SWCNTs obtained by atomic force microscopy (AFM) imaging. Our simulations illustrate that the multiple guanine defects introduced within a single ssDNA strand strongly interact to create a deep exciton trapping well, acting as a single hybrid trap. The emission decay from the distinctive trapping potential landscape is found to be biexponential for ssDNA-modified SWCNTs. We attributed the fast time component of the biexponential PL decay to the redistribution of exciton population among the lowest energy bright states and a manifold of dark states emerging from the coupling of multiple guanine defects. The long lifetime component in the biexponential decay, on the other hand, is attributed to the redistribution of exciton population among different exciton trapping sites that arise from the binding of multiple ssDNA strands along the nanotube axis. AFM measurements indicate that those trapping sites are separated on average by ∼8 nm along the nanotube axis.