Operando neutron reflectometry measurements were carried out to study the insertion of lithium into amorphous silicon film electrodes during cyclic voltammetry (CV) experiments at a scan rate of 0.01 mV s ⁻¹ .

Self-diffusion in intrinsic single crystalline germanium was investigated between 429 and 596 °C using G70e/Gnate isotope multilayer structures. The diffusivities were determined by neutron reflectometry from the decay of the first and third order Bragg peak. At high temperatures the diffusivities are in excellent agreement with literature data obtained by ion beam sputtering techniques, while considerably smaller diffusion lengths between 0.6 and 4.1 nm were measured. At lower temperatures the accessible range of diffusivities could be expanded to D≈1×10−25 m2 s−1, which is three orders of magnitude lower than the values measured by sputtering techniques. Taking into account available data on Ge self-diffusion, the temperature dependence is accurately described over nine orders of magnitude by a single Arrhenius equation. A diffusion activation enthalpy of 3.13±0.03 eV and a pre-exponential factor of 2.54×10−3 m2 s−1 for temperatures between 429 and 904 °C are obtained. Single vacancies are considered to prevail self-diffusion in Ge over the whole temperature range.

Neutron reflectometry is used to study in situ the intercalation of lithium into amorphous silicon electrodes. The experiments are done using a closed three-electrode electrochemical cell setup. As a working electrode, an about 40 nm thick amorphous silicon layer is used that is deposited on a 1 cm thick quartz substrate coated with palladium as a current collector. The counter electrode and the reference electrode are made of lithium metal. Propylene carbonate with 1 M LiClO₄ is used as an electrolyte. The utility of the cell is demonstrated during neutron reflectometry measurements where Li is intercalated at a constant current of 100 μA (7.8 μA cm⁻²) for different time steps. The results show (a) that the change in Li content in amorphous silicon and the corresponding volume expansion can be monitored, (b) that the formation of the solid electrolyte interphase becomes visible and (c) that an irreversible capacity loss is present.