Silicon
electrodes hold a promise of increasing the capacity of
lithium-ion batteries ten-fold. Yet, their commercial deployment is
hampered by large volume changes of silicon particles in response
to lithium insertion and extraction. Optimal design of porous silicon
structures, aimed at ameliorating this drawback, requires experimentation
guided by mathematical models of the chemomechanical behavior of silicon-anode
particles and their agglomerations. We present such a model that describes
the temporal evolution of a hollow or solid particle’s volume
and concomitant stresses, for both galvanostatic and potentiostatic
operating conditions. This model is used to optimize design parametersparticle
size, particle thickness, and charging profilesfor energy
density, while maintaining stable elastic operation. It accurately
predicts the experimentally observed value of the partial molar volume
of lithium in silicon. Our model also furnishes fundamental insights
into chemomechanical interactions in multiparticle electrode systems,
which are crucial for advancement of the silicon-electrode technology.