Analogy between electrochemical behaviour of thick silicon granular electrodes for lithium batteries and fine soils micromechanics

In this paper we study the influence of the distribution and the shape of the carbon conductive additives on the cyclability of thick silicon based composite electrodes. Results pinpoint the influence of carbon additives is not only to play on the electronic conductivity but also to play on the micromechanics (stress distribution) of the composite films. The lack of correlation between electrochemical performance and the macroscopic electronic conductivity of the pristine electrodes and the observation of repeated drops and jumps in capacity during cycling brought us to make an analogy between the silicon composite electrodes and cohesive granular materials such as fine soils media. Considering the collective mechanical behavior of a stack of silicon particles upon repeated volume variations shed a novel understanding to the electrochemical behavior of composite electrodes based on silicon and alloying materials and tells us how critically important is the design at the different scales (the particle, a few particles, the composite electrode, the cell) to engineer the mechanical stress and strain and improve cycle life. (C) 2014 Elsevier Ltd. All rights reserved.