Silicon is a promising material for high-energy anode materials for the next generation of lithium-ion batteries. The gain in specific capacity depends highly on the quality of the Si dispersion and on the size and shape of the nano-silicon. The aim of this study is to investigate the impact of the size/shape of Si on the electrochemical performance of conventional Li-ion batteries. The scalable synthesis processes of both nanoparticles and nanowires in the 10–100 nm size range are discussed. In cycling lithium batteries, the initial specific capacity is significantly higher for nanoparticles than for nanowires. We demonstrate a linear correlation of the first Coulombic efficiency with the specific area of the Si materials. In long-term cycling tests, the electrochemical performance of the nanoparticles fades faster due to an increased internal resistance, whereas the smallest nanowires show an impressive cycling stability. Finally, the reversibility of the electrochemical processes is found to be highly dependent on the size/shape of the Si particles and its impact on lithiation depth, formation of crystalline Li₁₅Si₄ in cycling, and Li transport pathways.

A versatile, low-cost and easily scalable synthesis method is presented for producing silicon nanowires (SiNWs) as a pure powder. It applies air-stable diphenylsilane as a Si source and gold nanoparticles as a catalyst and takes place in a sealed reactor at 420 °C (pressure <10 bar). Micron-sized NaCl particles, acting as a sacrificial support for the catalyst particles during NW growth, can simply be removed with water during purification. This process gives access to SiNWs of precisely controlled diameters in the range of 10 ± 3 nm with a high production yield per reactor volume (1 mg cm⁻³). The reaction was scaled up to 500 mg of SiNWs without altering the morphology or diameter. Adding diphenylphosphine results in SiNW n-type doping as confirmed by ESR spectroscopy and EDX analyses. The measured SiNW doping level closely follows the initial dopant concentration. Doping induces both an increase in diameter and a sharp increase of electrical conductivity for P concentrations >0.4%. When used in symmetric supercapacitor devices, 1% P-doped SiNWs exhibit an areal capacity of 0.25 mF cm⁻² and retention of 80% of the initial capacitance after one million cycles, demonstrating excellent cycling stability of the SiNW electrodes in the presence of organic electrolytes.

The galvanostatic charge–discharge (GCD) behaviour of silicon (Si) is known to depend strongly on morphology, cycling conditions and electrochemical environment. One common method for analysing GCD curves is through differential capacity, but the data processing required necessarily degrades the results. Here we present a method of extracting empirical information from the delithiation step in GCD data for Si at C-rates above equilibrium conditions. We find that the function is able to quickly and accurately determine the best fit to historical half-cell data on amorphous Si nanowires and thin films, and analysis of the results reveals that the function is capable of distinguishing the capacity contributions from the Li${}_{3.5}$Si and Li${}_2$Si phases to the total capacity. The method can also pick up small differences in the phase behaviour of the different samples, making it a powerful technique for further analysis of Si data from the literature. The method was also used for predicting the size of the reservoir effect (the apparent amount of Li remaining in the electrode), making it a useful technique for quickly determining voltage slippage and related phenomena. This work is presented as a starting point for more in-depth empirical analysis of Si GCD data.