Conducting polymers are envisioned to play a significant role in the development of organic matter based electrical energy conversion and storage systems. However, successful utilization of conducting polymers relies on a fundamental understanding of their inherent possibilities and limitations. In this report we studied the temperature dependence of the self-discharge in polypyrrole and show that the rate of self-discharge is kinetically controlled by a polymer intrinsic endergonic electron transfer reaction forming a reactive intermediate. We further show that this intermediate is intimately linked to a process known as overoxidation. This process is general for most, if not all, p-doped conducting polymers irrespective of medium. The results herein are therefore expected to significantly impact the development of future energy storage systems with conducting polymer based components.
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