Voltage Hysteresis of Silicon Nanoparticles: Chemo‐Mechanical Particle‐SEI Model

Abstract Silicon is a promising anode material for next‐generation lithium‐ion batteries. However, the volume change and the voltage hysteresis during lithiation and delithiation are two substantial drawbacks to their lifetime and performance. The reason for the voltage hysteresis in amorphous silicon nanoparticles covered by a solid‐electrolyte interphase (SEI) is investigated. Concentration gradients inside the nanoscale silicon cannot produce the massive stresses necessary to cause the reported voltage hysteresis. The chemo‐mechanical model shows that plastic deformation of the stiff, inorganic SEI during lithiation and delithiation reproduces the observed silicon open‐circuit voltage hysteresis. Additionally, the viscous behavior of the SEI explains the difference between the voltage hysteresis observed at low currents and after relaxation. It is concluded that the visco‐elastoplastic behavior of the SEI is the origin of the voltage hysteresis in silicon nanoparticle anodes. Thus, consideration of the SEI mechanics is crucial for further improvements.