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Summary  LiFePO 4 ‐based cathodes suffer from various degradation mechanisms, which influences the battery performance. In this paper, morphological and structural degradation phenomena in laboratory cathodes made of LiFePO 4  mixed with carbon black (CB) in a 1 mol/L LiPF 6  in EC : DMC (1:1 by weight) electrolyte are investigated by transmission electron microscopy at various preparation, assembling, storage, and cycling stages. High‐resolution transmission electron microscopy imaging shows that continuous SEI layers are formed on the LiFePO 4  particles and that both storage and cycling affect the formation. Additionally, loss of CB crystallinity, CB aggregation, and agglomeration is observed. Charge–discharge curves and impedance spectra measured during cycling confirm that these degradation mechanisms reduce the cathode conductivity and capacity. Copyright © 2016 John Wiley & Sons, Ltd.

A TEM study of morphological and structural degradation phenomena in LiFePO 4 ‐CB cathodes