Coupling In Situ TEM and Ex Situ Analysis to Understand Heterogeneous Sodiation of Antimony.

We employed an in situ electrochemical cell in the transmission electron microscope (TEM) together with ex situ time-of-flight, secondary-ion mass spectrometry (TOF-SIMS) depth profiling, and FIB-helium ion scanning microscope (HIM) imaging to detail the structural and compositional changes associated with Na/Na(+) charging/discharging of 50 and 100 nm thin films of Sb. TOF-SIMS on a partially sodiated 100 nm Sb film gives a Na signal that progressively decreases toward the current collector, indicating that sodiation does not proceed uniformly. This heterogeneity will lead to local volumetric expansion gradients that would in turn serve as a major source of intrinsic stress in the microstructure. In situ TEM shows time-dependent buckling and localized separation of the sodiated films from their TiN-Ge nanowire support, which is a mechanism of stress-relaxation. Localized horizontal fracture does not occur directly at the interface, but rather at a short distance away within the bulk of the Sb. HIM images of FIB cross sections taken from sodiated half-cells, electrically disconnected, and aged at room temperature, demonstrate nonuniform film swelling and the onset of analogous through-bulk separation. TOF-SIMS highlights time-dependent segregation of Na within the structure, both to the film-current collector interface and to the film surface where a solid electrolyte interphase (SEI) exists, agreeing with the electrochemical impedance results that show time-dependent increase of the films' charge transfer resistance. We propose that Na segregation serves as a secondary source of stress relief, which occurs over somewhat longer time scales.

Thermodynamically destabilized hydride formation in "bulk" Mg-AlTi multilayers for hydrogen storage.

Thermodynamic destabilization of MgH2 formation through interfacial interactions in free-standing Mg-AlTi multilayers of overall "bulk" (0.5 µm) dimensions with a hydrogen capacity of up to 5.5 wt% is demonstrated. The interfacial energies of Mg-AlTi and Mg-Ti (examined as a baseline) are calculated to be 0.81 and 0.44 J m(-2). The enhanced interfacial energy of AlTi opens the possibility of creating ultrathin alloy interlayers that provide further thermodynamic improvements in metal hydrides.

ALD TiO2 coated silicon nanowires for lithium ion battery anodes with enhanced cycling stability and coulombic efficiency.

We demonstrate that silicon nanowire (SiNW) Li-ion battery anodes that are conformally coated with TiO2 using atomic layer deposition (ALD) show a remarkable performance improvement. The coulombic efficiency is increased to ∼99%, among the highest ever reported for SiNWs, as compared to 95% for the baseline uncoated samples. The capacity retention after 100 cycles for the nanocomposite is twice as high as that of the baseline at 0.1 C (60% vs. 30%), and more than three times higher at 5 C (34% vs. 10%). We also demonstrate that the microstructure of the coatings is critically important for achieving this effect. Titanium dioxide coatings with an as-deposited anatase structure are nowhere near as effective as amorphous ones, the latter proving much more resistant to delamination from the SiNW core. We use TEM to demonstrate that upon lithiation the amorphous coating develops a highly dispersed nanostructure comprised of crystalline LiTiO2 and a secondary amorphous phase. Electron energy loss spectroscopy (EELS) combined with bulk and surface analytical techniques are employed to highlight the passivating effect of TiO2, which results in significantly fewer cycling-induced electrolyte decomposition products as compared to the bare nanowires.

Effect of alloying magnesium with chromium and vanadium on hydrogenation kinetics studied with neutron reflectometry.

The effect of chromium and vanadium alloying on the hydrogenation of a magnesium thin film is studied by neutron reflectometry. Immediate formation of a blocking MgD(2) layer is observed in pure Mg, however in the alloyed film deuteration is rapid and almost completely homogeneous.