Abstract Understanding and tracking battery degradation mechanisms and adapting its operation have become a necessity in order to enhance battery durability. A novel use of differential thermal voltammetry (DTV) is presented as an in-situ state-of-health (SOH) estimator for lithium-ion batteries. Accelerated ageing experiments were carried on 5Ah commercial lithium-ion polymer cells operated and stored at different temperature and loading conditions. The cells were analysed regularly with various existing in-situ diagnosis methods and the novel DTV technique to determine their SOH. The diagnosis results were used collectively to elaborate the degradation mechanisms inside the cells. The DTV spectra were decoupled into individual peaks, which each represent particular phases in the negative and positive electrode combined. The peak parameters were used to quantitatively analyse the battery SOH. A different cell of the same chemistry with unknown degradation history was then analysed to explore how the cell degraded. The DTV technique was able to diagnose the cell degradation without relying on supporting results from other methods nor previous cycling data.