On the Morphological Evolution with Cycling of a Ball-Milled Si Slag-Based Electrode for Li-Ion Batteries

A Si/SiC/SiO2 (53/44/3 wt.%) composite is evaluated as an anode material for Li-ion batteries. This material, a result of the high-energy ball-milling of a by-product of the carbothermal reduction of silica (Si slag), is predominantly made up of micrometric particles of amorphous or short-range order Si in which submicrometric SiC inclusions are dispersed. Its capacity is 860 mAh g−1 (1.7 mAh cm−2) after 200 cycles in half-cell configuration and 1.6 mAh cm−2 after 70 cycles in full-cell. The SiC component is not electroactive for lithiation but plays a key role in the electrode stability by preventing the formation of the c-Li15Si4 phase, known to accelerate electrode degradation. It is shown that capacity decay with cycling mainly originates from solid electrolyte interphase (SEI) growth rather than particle disconnections. Complementary wide angle X-ray scattering (WAXS) analyses confirm the SEI grows alongside cycling and allows for the highlighting of its major components, namely, Li2CO3 and LiF. The morphological evolution of the electrode upon cycling is studied by electrochemical dilatometry, operando optical microscopy, and focused ion beam (FIB) and broad ion beam (BIB) scanning electron microscopy (SEM). No particle cracking is observed. However, reconstructed 3D imaging of the electrodes before and after 10 and 200 cycles clearly shows that the particles progressively evolve a dendritic structure. The SEI grows on and within the particles and induces a significant decrease in the electrode’s porosity and an increase in its thickness.