Stoichiometry-Controlled Reversible Lithiation Capacity in Nanostructured Silicon Nitrides Enabled by in Situ Conversion Reaction.

In modern Li-based batteries, alloying anode materials have the potential to drastically improve the volumetric and specific energy storage capacity. For the past decade silicon has been viewed as a "Holy Grail" among these materials; however, severe stability issues limit its potential. Herein, we present amorphous substoichiometric silicon nitride (SiNx) as a convertible anode material, which allows overcoming the stability challenges associated with common alloying materials. Such material can be synthesized in a form of nanoparticles with seamlessly tunable chemical composition and particle size and, therefore, be used for the preparation of anodes for Li-based batteries directly through conventional slurry processing. Such SiNx materials were found to be capable of delivering high capacity that is controlled by the initial chemical composition of the nanoparticles. They exhibit an exceptional cycling stability, largely maintaining structural integrity of the nanoparticles and the complete electrodes, thus delivering stable electrochemical performance over the course of 1000 charge/discharge cycles. Such stability is achieved through the in situ conversion reaction, which was herein unambiguously confirmed by pair distribution function analysis of cycled SiNx nanoparticles revealing that active silicon domains and a stabilizing Li2SiN2 phase are formed in situ during the initial lithiation.

Morphology engineering of silicon nanoparticles for better performance in Li-ion battery anodes.

Amorphous silicon nanoparticles were synthesized through pyrolysis of silane gas at temperatures ranging from 575 to 675 °C. According to the used temperature and silane concentration, two distinct types of particles can be obtained: at 625 °C, spherical particles with smooth surface and a low degree of aggregation, but at a higher temperature (650 °C) and lower silane concentration, particles with extremely rough surfaces and high degree of aggregation are found. This demonstrates the importance of the synthesis temperature on the morphology of silicon particles. The two types of silicon nanoparticles were subsequently used as active materials in a lithium half cell configuration, using LiPF6 in an alkylcarbonate-based electrolyte, in order to investigate the impact of the particles morphology on the cycling performances of silicon anode material. The difference in morphology of the particles resulted in different volume expansions, which impacts the solid electrolyte interface (SEI) formation and, as a consequence, the lifetime of the electrode. Half-cells fabricated from spherical particles demonstrated almost 70% capacity retention for over 300 cycles, while the cells made from the rough, aggregated particles showed a sharp decrease in capacity after the 20th cycle. The cycling results underline the importance of Si particle engineering and its influence on the lifetime of Si-based materials.