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Carbon based double layer capacitors with aprotic electrolyte solutions: the possible role of intercalation/insertion processes

Abstract

The extraordinary stability and cycle life performance of today's electrochemical double-layer capacitors (EDLCs) are generally ascribed to the fact that charge storage in activated carbon (AC) is based on pure double-layer charging. In contrast, Faradaic charge-transfer reactions like those occurring in batteries are often connected with dimensional changes, which can affect the cycle life of these storage devices. Here we report the charge-induced height change of an AC electrode in an aprotic electrolyte solution, 1mol/l (C2H5)4NBF4 (TEABF4) in acetonitrile. The results are compared with those obtained for a graphite electrode in the same electrolyte. For both electrodes, we observe an expansion/contraction of several percent for a potential window of ±2V vs. the immersion potential (ip). For the EDLC electrode, significant expansion starts at about 1V remote from the ip and hence is well within the normal EDLC operation range. For the graphite electrode, the height changes are unambiguously caused by intercalation/deintercalation of both anions and cations. The close analogies between the graphite and the EDLC electrode suggest that ion intercalation or insertion processes might play a major role for charge storage, self discharge, cyclability, and the voltage limitation of EDLC

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