Effect of Stress on the Electrochemical Response of Amorphous Silicon Electrodes

Abstract

Silicon electrodes for lithium-ion batteries exhibit a theoretical capacity ten times higher than that of the graphite electrodes currently used in commercial systems. When lithiated/delithiated, silicon experiences stresses on the order of one GPa, inducing the damage of the material, which results in poor cyclability. Concurrently, irreversible continuum thermodynamics predicts that these stresses affect the lithiation itself in different ways for monophasic and biphasic lithiation (progressive invasion of the electrode by a lithiated phase of given composition) [1,2]. When lithiation takes place homogeneously (without phase transformation), mechanical stresses affect lithiation through their effect on the chemical potential of diffusing lithium (Larché-Cahn theory). On the other hand, when lithiation is biphasic, mechanical stresses affect lithiation through an effect on both chemical potential of lithium and thermodynamic driving force acting on the phase boundary. This coupling has first been probed experimentally in homogeneous lithiation using a method where the stress state of silicon is modified indirectly through incremental delithiation [3].In this work, we investigate the interplay between the electrochemical state (electrode potential and current density) of an amorphous silicon electrode and its stress state. The electrochemical response of the amorphous silicon thin film deposited on a stainless steel substrate has been recorded under varying mechanical loading during lithiation and delithiation cycles. The mechanical loading is applied by deforming elastically the steel substrate of the amorphous silicon thin film, which allows us to directly probe the contribution of mechanics to the lithiation/delithiation processes. When carried out under galvanostatic conditions, incremental changes in stress lead to instantaneous change in the electrode potential. Experimental results from uniaxial tensile tests show that an applied strain of 0.3%, resulting in changes in stress in silicon of ~ 200-300 MPa, induces a potential variation on the order of 2.5 mV. Stress-induced changes in the potential are measured for the biphasic first lithiation, as well as subsequent monophasic lithiation and delithiation sequences at different states of charge. These results are discussed within the context of continuum thermodynamic theories of the coupling between transport of chemical species and mechanical stress.[1] A. F. Bower, E. Chason, P. R. Guduru, B. W. Sheldon, Acta Mater. 98 (2015) 229-241.[2] A. F. Bower, P. R. Guduru, E. Chason, Int. J. Solids Struct. 69 (2015) 328-342.[3] V. A. Sethuraman, V. Srinivasan, A. F. Bower, P. R. Guduru, J. Electrochem. Soc. 157 (2010) A1253.