Expanding the active charge carriers of polymer electrolytes in lithium-based batteries using an anion-hosting cathode

Ionic-conductive polymers are appealing electrolyte materials for solid-state lithium-based batteries. However, these polymers are detrimentally affected by the electrochemically-inactive anion migration that limits the ionic conductivity and accelerates cell failure. To circumvent this issue, we propose the use of polyvinyl ferrocene (PVF) as positive electrode active material. The PVF acts as an anion-acceptor during redox processes, thus simultaneously setting anions and lithium ions as effective charge carriers. We report the testing of various Li||PVF lab-scale cells using polyethylene oxide (PEO) matrix and Li-containing salts with different anions. Interestingly, the cells using the PEO-lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) solid electrolyte deliver an initial capacity of 108 mAh g⁻¹ at 100 μA cm⁻² and 60 °C, and a discharge capacity retention of 70% (i.e., 70 mAh g⁻¹) after 2800 cycles at 300 μA cm⁻² and 60 °C. The Li|PEO-LiTFSI|PVF cells tested at 50 μA cm⁻² and 30 °C can also deliver an initial discharge capacity of around 98 mAh g⁻¹ with an electrolyte ionic conductivity in the order of 10⁻⁵S cm⁻¹.