Abstract

Various Si/carbon/polymer composite electrodes were prepared to better understand the influence of the Si−polymer interactions on the stability of the Li−Si reaction and especially the superior performances of CMC-based (carboxy−methyl−cellulose) composites despite the large volume changes of the Si particles upon cycling. Via the modification of the composites formulation, the nature of the polymer, the nature and the amount of the substituting groups and the surface chemistry of the Si particles, together with the use of various characterization techniques (TEM, SEM, NMR−MAS, infrared spectroscopy, TGA, etc.) we could propose that the performances of the Si/Csp/CMC composite electrodes are nested in both the porous texture of the electrode and in the nature of the Si−polymer chemical bonding. A self-healing process of the rather strong Si−CMC hydrogen bonding which can accommodate textural stresses and can evolve during cycling is proposed to be critical for Si-based electrode performances. This better understanding leads to the design of Si-based electrodes with capacity retention reaching 1000 mAh/g of composite (i.e., full Si capacity) for at least 100 cycles and with a Coulombic efficiency close to 99.9% per cycle. Owing to these new aspects, we have now a deeper insight of the specific effects of the CMC binder, than could be successfully extended to other metals (Sn, Ge, Sb).