Future device applications will dictate increases in the energy density of batteries, which may be accomplished by incorporating high capacity electroactive materials into composite electrodes where all the electroactive material is electrochemically accessible and the mass and volume contributions of passive components are minimized. Electroactive materials are incorporated into batteries through the fabrication of composite electrodes, where several additives may be used to enhance conductivity and to mechanically bind the components. Typically, an electrically conductive carbon additive (e.g. acetylene black or graphite) and a polymer binder (e.g. PVDF and PTFE) are mixed with the electroactive material to form a composite electrode. Electrically conducting polymers are intriguing as composite electrode additives since conceptually they can fulfill the roles of both carbon and binder.

Magnetite is a naturally occurring mineral found in the earth’s crust; therefore, it is abundant, environmentally friendly, cheap, and non-toxic. Magnetite is also easy to synthesize and can be prepared through simple, non-hazardous techniques such as through a facile aqueous co-precipitation method. Complete reduction of magnetite involves the transfer of 8 electrons, providing opportunity for an impressive capacity of 925 mAh/g. Notably, the initial reactions are insertion reactions where the lithium ion can insert into the Fe₃O₄ structure with minimal structural distortion, while upon further reduction, a conversion reaction occurs generating Fe metal and Li₂O as products of full discharge.

To further probe the role of the electrically conductive polymer in the mesoscale (bulk) properties of composite electrodes, this study focuses on the Fe₃O₄ conversion reaction and its relationship to the electrically conductive polymer binder, PPy, including a detailed study of composite electrodes with nanoscale Fe₃O₄ and PPy. Magnetite, Fe₃O₄, with 6% and 20% polypyrrole (PPy) was used to prepare composite electrodes with and without added carbon.

Galvanostatic cycling and Electrochemical Impedance Spectroscopy (EIS) measurements were used in tandem to determine delivered capacity, capacity retention, and the related impedance at various stages of discharge and charge. Further, the reversibility of Fe₃O₄ to iron metal conversion observed during discharge was quantitatively assessed, ex situ, using X-ray Absorption Spectroscopy (XAS). The Fe₃O₄ composite containing the largest weight fraction of PPy (20 wt%) with added carbon demonstrated reduced irreversible capacity on initial cycles and improved cycling stability over 50 cycles. This study illustrated the beneficial role of PPy addition to Fe₃O₄ based electrodes partially related to improved electrical conductivity and also to improved ion transport related to the formation of a more favorable surface electrolyte interphase (SEI).