Polysiloxane Pyrolysis

Different polysiloxanes were pyrolyzed to make silicon oxycarbide glasses which have been shown to be possible candidates for anode materials of Li-ion batteries. The decomposition process during pyrolysis was studied using a thermal gravimetric analyzer connected to a residual gas analyzer for three representative polymers. No silicon- or oxygen-containing gases were observed during pyrolysis. The stoichiometry of all of the final chars was measured and found to agree well with predictions calculated using the initial polymer stoichiometry, the ceramic yield, and the fact that only carbon and hydrogen atoms were eliminated during pyrolysis. For three chars with identical stoichiometry at 1000 °C, prepared from three different polymers, the local chemical environment of the silicon was studied as a function of pyrolysis temperature by X-ray absorption (XAS) near the silicon K-edge. As the samples are heated, the XAS spectra eventually become identical, once the different labile species have been eliminated, suggesting that the properties of the char are dependent mainly on its stoichiometry and not on the initial composition of the polymer precursor. The bulk properties of these three chars prepared at 1000 °C were also studied by X-ray diffraction and by electrochemical methods which showed them to be identical.