Influence of Polymorphism on the Electrochemical Behavior of Dilithium (2,3-Dilithium-oxy)-terephthalate vs. Li

Abstract

Organic electrode materials offer obvious opportunities to promote cost-effective and environmentally friendly rechargeable batteries. Over the last decade, tremendous progress has been made thanks to the use of molecular engineering focused on the tailoring of redox-active organic moieties. However, the electrochemical performance of organic host structures relies also on the crystal packing, like the inorganic counterparts, which calls for further efforts in terms of crystal chemistry to make a robust redox-active organic center electrochemically efficient in the solid state. Following our ongoing research aiming at elaborating lithiated organic cathode materials, we report herein on the impact of polymorphism on the electrochemical behavior of dilithium (2,3-dilithium-oxy-)terephthalate vs. Li. Having isolated dilithium (3-hydroxy-2-lithium-oxy)terephthalate through an incomplete acid-base neutralization reaction, its subsequent thermally induced decarboxylation mechanism led to the formation of a new polymorph of dilithium (2,3-dilithium-oxy-)terephthalate referred to as Li4-o-DHT (β-phase). This new phase is able to operate at 3.1 V vs. Li+/Li, which corresponds to a positive potential shift of +250 mV compared to the other polymorph formerly reported. Nevertheless, the overall electrochemical process characterized by a sluggish biphasic transition is impeded by a large polarization value limiting the recovered capacity upon cycling.