Tunable Order in Alginate/Graphene Biopolymer Nanocomposites

We report on highly aligned graphene oxide or graphene sheets inside an alginate matrix and their structure obtained for various compositions. The order of the platelet particles with respect to one another has been verified by environmental scanning electron microscopy (ESEM) and 2-dimensional X-ray diffraction (2D XRD). The microscopic order within the platelet particles has been analyzed by X-ray diffraction (XRD) measurements in the Bragg–Brentano reflection configuration as well as in Debye–Scherrer diffraction mode. The azimuthal angle intensity profiles obtained from 2D XRD analysis have been fit to Maier–Saupe and affine deformation model predictions, and the affine deformation model proved to be the most reliable to quantify the order parameter ⟨<i>P</i>₂⟩ values of graphene oxide/sodium alginate and graphene/calcium alginate composites with different weight fractions of the filler. The ⟨<i>P</i>₂⟩ values for graphene oxide/sodium alginate composites were found to show little dependence on the concentration of graphene sheets above ∼10 wt %, with a maximum ⟨<i>P</i>₂⟩ value of 0.8 at 25 wt % graphene oxide inside the sodium alginate matrix. The alignment of graphene sheets inside the calcium alginate matrix has been observed to be lower, with an average ⟨<i>P</i>₂⟩ value of 0.7. We have not observed preferred orientation of graphene sheets inside the barium alginate matrix. The formation of a highly aligned graphene oxide/sodium alginate composite structure has been explained by the affine deformation model, whereupon drying the developed yield stress causes sheets to align in-plane with the polymer matrix. The impaired orientation of graphene sheets inside the calcium alginate matrix and absence of orientation in the barium alginate matrix have been explained by the structure development in the polymer matrix itself due to metal-ion-induced cross-linking

Use of Nano Seed Crystals To Control Peroxide Morphology in a Nonaqueous Li–O₂ Battery

The high theoretical energy density of Li–O₂ batteries as required for electrification of transport has pushed Li–O₂ research to the forefront. The poor cyclability of this system due to incomplete Li₂O₂ oxidation is one of the major hurdles to be crossed if it is ever to deliver a high reversible energy density. Here we present the use of nano seed crystallites to control the size and morphology of the Li₂O₂ crystals. The evolution of the Li₂O₂ lattice parameters during <i>operando</i> X-ray diffraction demonstrates that the hexagonal NiO nanoparticles added to the activated carbon electrode act as seed crystals for equiaxed growth of Li₂O₂, which is confirmed by scanning electron microscopy energy-dispersive X-ray spectroscopy (SEM-EDX) elemental maps also showing preferential formation of Li₂O₂ on the NiO surface. Even small amounts of NiO (∼5 wt %) particles act as preferential sites for Li₂O₂ nucleation, effectively reducing the average size of the primary Li₂O₂ crystallites and promoting crystalline growth. This is supported by first principle calculations, which predict a low interfacial energy for the formation of NiO–Li₂O₂ interfaces. The eventual cell failure appears to be the consequence of electrolyte side reactions, indicating the necessity of more stable electrolytes. The demonstrated control of the Li₂O₂ crystallite growth by the rational selection of appropriate nano seed crystals appears to be a promising strategy to improve the reversibility of Li–air electrodes