Lithium sulfur (Li-S) batteries are an important next generation high energy density battery technology. However, the phenomenon known as the polysulfide shuttle causes accelerated degradation, reduced Coulombic efficiency and increased heat generation, particularly towards the end of charge. The real-time detection of the onset of shuttle during charge would improve the safety and increase cycle life of Li-S batteries in real applications. In this study, we demonstrate that the Differential Thermal Voltammetry (DTV) technique can be used for tracking shuttle during Li-S charging. By combining voltage and temperature measurements, DTV is shown to be sensitive to the magnitude of shuttle. We demonstrate significant differences in the DTV curves for Li-S cells charged at different currents and temperatures. Quantitative interpretations of the experimental DTV curves are performed through a thermally-coupled zero-dimensional Li-S model. The DTV technique, together with the model, is a promising tool for real-time detection of shuttle in applications, to inform control algorithms for deciding the end of charging, thus preventing excessive degradation and charge inefficiency.