Electrode Modification by Laser Ablation to Overcome Mechanical and Scalability Limitations of Solid-State Prealkylation of Electrode Architectures
In this work, laser ablation of Si electrode surfaces is utilized to provide localized strain relief during the Solid State Prealkylation of Electrode Architectures (SPEAR) process, in addition to volumetric expansion relief in the form of free volume channels across the electrode. A hexagonal mesh patterning was employed via laser ablation, where the hexagonal diameter (pitch) was varied from 250 to 1000 µm. It was demonstrated that these channels serve as expansion voids, accommodating the increase in electrode thickness observed during SPEAR and preventing cracking at the electrode surface. Optical microscopy and Raman mapping confirm that Li diffusion is the rate-limiting solid-state process, requiring a 24 h rest period to achieve homogeneous LixSi alloying through the electrode bulk. Electrochemical evaluations in full cells show that a 1000 μm pitch pattern yields a high initial discharge capacity of 2485 mA h g–1 and 86.4% capacity retention after 80 cycles, whereas smaller pitches (<500 μm) result in lithium plating at 4.1 V in full cells paired with NMC 811 due to excessive current collector exposure from the ablation process. XPS analysis reveals that the laser treatment modifies the electrode surface by increasing the Si–O and C–O species, changing the SEI composition observed via an increase in fluorophosphates upon cycling.