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The Li-S batteries are a prospective battery technology, which despite to its currently remaining drawbacks offers useable performance and interesting features. The polysulfide shuttle mechanism, a characteristic phenomenon for the Li-S batteries, causes a significant self-discharge at higher state-of-charge (SOC) levels, which leads to the energy dissipation of cells with higher charge. In an operation of series-connected Li-S cells, the shuttle mechanism results into a self-balancing effect which is studied here. A model for prediction of the self-balancing effect is proposed in this work and it is validated by experiments. Our results confirm the self-balancing feature of Li-S cells and illustrate their dependence on various conditions such as temperature, charging limits and idling time at high SOC.