We report direct observation of an unexpected anisotropic swelling of Si nanowires during lithiation against either a solid electrolyte with a lithium counter-electrode or a liquid electrolyte with a LiCoO(2) counter-electrode. Such anisotropic expansion is attributed to the interfacial processes of accommodating large volumetric strains at the lithiation reaction front that depend sensitively on the crystallographic orientation. This anisotropic swelling results in lithiated Si nanowires with a remarkable dumbbell-shaped cross section, which develops due to plastic flow and an ensuing necking instability that is induced by the tensile hoop stress buildup in the lithiated shell. The plasticity-driven morphological instabilities often lead to fracture in lithiated nanowires, now captured in video. These results provide important insight into the battery degradation mechanisms.

From in situ transmission electron microscopy (TEM) observations, we present direct evidence of lithiumassisted welding between physically contacted silicon nanowires (SiNWs) induced by electrochemical lithiation and delithiation. This electrochemical weld between two SiNWs demonstrates facile transport of lithium ions and electrons across the interface. From our in situ observations, we estimate the shear strength of the welded region after delithiation to be approximately 200 MPa, indicating that a strong bond is formed at the junction of two SiNWs. This welding phenomenon could help address the issue of capacity fade in nanostructured silicon battery electrodes, which is typically caused by fracture and detachment of active materials from the current collector. The process could provide for more robust battery performance either through self-healing of fractured components that remain in contact or through the formation of a multiconnected network architecture.

Stability and high energy densities are essential qualities for emerging battery electrodes. Because of its high specific capacity, silicon has been considered a promising anode candidate. However, the several-fold volume changes during lithiation and delithiation leads to fractures and continuous formation of an unstable solid-electrolyte interphase (SEI) layer, resulting in rapid capacity decay. Here, we present a carbon-silicon-carbon (C@Si@C) nanotube sandwich structure that addresses the mechanical and chemical stability issues commonly associated with Si anodes. The C@Si@C nanotube array exhibits a capacity of ∼2200 mAh g(-1) (∼750 mAh cm(-3)), which significantly exceeds that of a commercial graphite anode, and a nearly constant Coulombic efficiency of ∼98% over 60 cycles. In addition, the C@Si@C nanotube array gives much better capacity and structure stability compared to the Si nanotubes without carbon coatings, the ZnO@C@Si@C nanorods, a Si thin film on Ni foam, and C@Si and Si@C nanotubes. In situ SEM during cycling shows that the tubes expand both inward and outward upon lithiation, as well as elongate, and then revert back to their initial size and shape after delithiation, suggesting stability during volume changes. The mechanical modeling indicates the overall plastic strain in a nanotube is much less than in a nanorod, which may significantly reduce low-cycle fatigue. The sandwich-structured nanotube design is quite general, and may serve as a guide for many emerging anode and cathode systems.

A generalized hydrothermal strategy for fabricating three-dimensional (3D) battery electrodes is presented. The hydrothermal growth deposits electrochemically active nanomaterials uniformly throughout the complex 3D mesostructure of the scaffold. Ni inverse opals coated with SnO2 nanoparticles or Co3O4 nanoplatelets, and SiO2 inverse opals coated with Fe3O4 are fabricated, all of which show attractive properties including good capacity retention and C-rate performances.

Spiropyran molecular switches, in conjunction with transition metal ions, are shown to operate as reversible polymer cross-linkers. Solutions containing a spiropyran-functionalized polymer and transition metal ions underwent reversible thermally triggered (light-triggered) transient network formation (disruption) driven by the association (dissociation) of metal–ligand cross-links. Heat triggers metal-ion-mediated cross-linking via thermal isomerization of spiropyran to its open, merocyanine form, and exposure to visible light triggers dissociation of polymer cross-links. Cross-linking is found to depend on both the valence of the ion as well as the molar ratio of spiropyran to metal salt. We envision this to be a starting point for the design of many types of reversible, stimuli-responsive polymers, utilizing the fact that spiropyrans have been shown to respond to a variety of stimuli including heat, light, pH, and mechanical force.