PYROLYZED POLYSILOXANES FOR USE AS ANODE MATERIALS IN LITHIUM-ION BATTERIES

More than sixty siloxane polymers containing various organofunctional siloxane units were synthesized. The synthesized siloxane polymers wer e pyrolyzed in inert gas at 1000 degrees C. Chemical analysis showed t hat the products of pyrolysis were distributed over a well-defined reg ion in the Si-C-O Gibbs phase diagram. The electrochemical and structu ral properties of these materials were measured using coin-type test c ells and x-rap powder diffraction, respectively. The most interesting materials are found near the line in the Si-C-O Gibbs triangle connect ing carbon to SiO1.3. Materials with the largest reversible specific c apacity for lithium (about 900 mAh/g) are on this line and were at abo ut 43% carbon, 32% oxygen, and 25% silicon (atomic percent). Materials which were almost pure carbon showed diffraction patterns characteris tic of disordered carbons. Along the line from carbon to SiO1.3 the sa mple structure can be described as a mixture of single or small groups of graphene sheets mixed with regions of Si-C-O amorphous glass. The amount and composition of the glass changed according to the overall s ample composition. Moving from carbon to SiO1.3, the reversible capaci ty first rises from about 340 mAh/g for pure carbon, to a maximum of 9 00 mAh/g near 50% carbon, and then falls to near zero mAh/g at 0% carb on. This suggests that the amorphous glass can reversibly react with l ithium, provided the carbon is present to provide a path for electrons and Li ions. However, the hysteresis in the voltage profile(differenc e between charge and discharge voltages) and the irreversible capacity increase almost linearly along this line. There is a clear correlatio n between both the irreversible capacity and hysteresis in these mater ials with their oxygen content. Along the line connecting carbon to si licon, the reversible capacity rises from 340 mAh/g for pure carbon to about 600 mAh/g for samples with about 15 atomic percent Si. It then decreases to near zero as the composition nears SiC. Along the C-SiC l ine, the irreversible capacities remain below about 200 mAh/g. We are quite convinced that optimized silicon-containing carbons can be good alternatives to pure carbons as anode materials in lithium-ion batteri es.