High-Density and Robust Charge Storage with Poly(anthraquinone-substituted norbornene) for Organic Electrode-Active Materials in Polymer-Air Secondary Batteries

摘要

An excellent functional group tolerance of ruthenium complex catalysts for olefin metathesis gave rise to ring-opening polymerization of norbornene functionalized with redox-active anthraquinone (AQ) pendants, yielding a high-molecular-weight and processable polynorbornene with large redox capacity. A thin layer of the polymer cast on current collectors showed reversible redox reaction at -0.85 V vs Ag/AgCl when immersed in basic aqueous electrolyte solutions. Good cycle performance was observed with a capacity comparable to the formula weight-based theoretical density of 212 mAh/g, which was the largest among those for the previously reported redox-active polynorbornenes. This suggested that all of the AQ units in the layer were redox-active, that electroneutralization was accomplished by successive compensation of counterions throughout the layer, and that the mechanical strength of the polymer layer prevented dissolution or exfoliation from the current collector surface. A robust polymer-air secondary battery with the high capacity was fabricated by using the polymer layer as the anode-active material. The battery showed a discharge voltage of 0.68 V and long life of over 300 cycles of charging/discharging, maintaining the moderate energy density of 143 mWh/g.