Georgiana Sandu

Surface Coating Mediated Swelling and Fracture of Silicon Nanowires during Lithiation

Surface passivation of silicon anodes is an appealing design strategy for the development of reliable, high-capacity lithium-ion batteries. However, the structural stability of the coating layer and its influence on the lithiation process remain largely unclear. Herein, we show that surface coating mediates the swelling dynamics and the fracture pattern during initial lithiation of crystalline silicon nanopillars. We choose conformally nickel coated silicon architectures as a model system. Experimental findings are interpreted based on a chemomechanical model. Markedly different swelling and fracture regimes have been identified, depending on the coating thickness and silicon nanopillar diameter. Nanopillars with relatively thin coating display anisotropic swelling similar to pristine nanopillars, but with different preferred fracture sites. As the coating thickness increases, the mechanisms become isotropic, with one randomly oriented longitudinal crack that unzips the core-shell structure. The morphology of cracked pillars resembles that of a thin-film electrode on a substrate, which is more amenable to cyclic lithiation without fracture. The knowledge provided here helps clarify the cycling results of coated nanosilicon electrodes and further suggests design rules for better performance electrodes through proper control of the lithiation and fracture.

Mechanochemical Synthesis of PEDOT:PSS Hydrogels for Aqueous Formulation of Li-Ion Battery Electrodes

Water-soluble binders can enable greener and cost-effective Li-ion battery manufacturing by eliminating the standard fluorine-based formulations and associated organic solvents. The issue with water-based dispersions, however, remains the difficulty in stabilizing them, requiring additional processing complexity. Herein, we show that mechanochemical conversion of a regular poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) water-based dispersion produces a hydrogel that meets all the requirements as binder for lithium-ion battery electrode manufacture. We particularly highlight the suitable slurry rheology, improved adhesion, intrinsic electrical conductivity, large potential stability window and limited corrosion of metal current collectors and active electrode materials, compared to standard binder or regular PEDOT:PSS solution-based processing. When incorporating the active materials, conductive carbon and additives with PEDOT:PSS, the mechanochemical processing induces simultaneous binder gelation and fine mixing of the components. The formed slurries are stable, show no phase segregation when stored for months, and produce highly uniform thin (25 μm) to very thick (500 μm) films in a single coating step, with no material segregation even upon slow drying. In conjunction with PEDOT:PSS hydrogels, technologically relevant materials including silicon, tin, and graphite negative electrodes as well as LiCoO2, LiMn2O4, LiFePO4, and carbon-sulfur positive electrodes show superior cycling stability and power-rate performances compared to standard binder formulation, while significantly simplifying the aqueous-based electrode assembly.

Kinked silicon nanowires-enabled interweaving electrode configuration for lithium-ion batteries

A tri-dimensional interweaving kinked silicon nanowires (k-SiNWs) assembly, with a Ni current collector co-integrated, is evaluated as electrode configuration for lithium ion batteries. The large-scale fabrication of k-SiNWs is based on a procedure for continuous metal assisted chemical etching of Si, supported by a chemical peeling step that enables the reuse of the Si substrate. The kinks are triggered by a simple, repetitive etch-quench sequence in a HF and H2O2-based etchant. We find that the inter-locking frameworks of k-SiNWs and multi-walled carbon nanotubes exhibit beneficial mechanical properties with a foam-like behavior amplified by the kinks and a suitable porosity for a minimal electrode deformation upon Li insertion. In addition, ionic liquid electrolyte systems associated with the integrated Ni current collector repress the detrimental effects related to the Si-Li alloying reaction, enabling high cycling stability with 80% capacity retention (1695 mAh/gSi) after 100 cycles. Areal capacities of 2.42 mAh/cm2 (1276 mAh/gelectrode) can be achieved at the maximum evaluated thickness (corresponding to 1.3 mgSi/cm2). This work emphasizes the versatility of the metal assisted chemical etching for the synthesis of advanced Si nanostructures for high performance lithium ion battery electrodes.

Surveying colloid sedimentation by coplanar waveguides

By using coplanar waveguides, direct access to the dielectric properties of aqueous solutions of polystyrene beads with different diameters from 330 nm to 10 μm is provided. The relative variation of the transmission parameter with respect to water is monitored, ranging from [Formula: see text] obtained for a 9.5% solution with 330 nm diameter beads to ∼22% for 10 μm diameter particles at the same concentration. To highlight its applicability in biosensing, the technique was further employed to survey the clustering between biotin and streptavidin-coated beads. The transmission parameter displays a ∼50% increase for mixtures containing nine volumes of biotin and one volume of streptavidin-modified beads (4.5 ng μl(-1) of streptavidin) and reaches ∼400% higher values when equal volumes of biotin and streptavidin-coated beads (22.5 ng μl(-1) of streptavidin) were mixed.