Bisthiazolyl Quinones: Stabilizing Organic Electrode Materials with Sulfur-Rich Thiazyl Motifs

Abstract

Organic electrode materials have emerged as attractive alternatives to electrodes in lithium-ion batteries produced from toxic and unsustainably sourced transition metals. However, low-molecular-weight organic compounds still lack the cycling stability and high-rate capability found in transition-metal electrodes. Herein, we report S-rich thiazyl moieties as a new design feature for small-molecule organic electrode materials. Our findings suggest that S-rich thiazyl moieties engender strong intermolecular interactions that contribute to the insolubility and fast charging of low-molecular-weight quinones. This is demonstrated by the contrasting performance of three isomorphic bisthiazolyl quinones in the solid state: the quinone with the strongest intermolecular interactions can be cycled at a high rate of 10 C for 400 cycles with a 94% capacity retention, while those with weak intermolecular interactions suffer from dissolution and low cycling stabilities (<20 cycles). Our study reveals that S-rich thiazyl moieties may be used to design low-molecular-weight organic electrode materials to achieve long cycle life and fast electrode kinetics.

Weak Intermolecular Interactions for Strengthening Organic Batteries

“…For example, the SÁÁÁS interactions may also reduce the solubility of the materials and led to enhanced cyclability of the batteries. [84,85] However, materials with these intermolecular interactions usually showed relatively low cycle life, probably due to the comparatively weaker intensity of the interactions.…”

2D Coordination Network of Trioxotriangulene with Multiple Redox Abilities and Its Rechargeable Battery Performance

“…On the other hand, in the case of 3 , in which molecules were connected by halogen bonds in the crystal, elution of the active material into the electrolyte was sufficiently suppressed, and cycle performance was greatly improved ( C TOT = 225 mA h g −1 at 1st cycle and C TOT = 159 mA h g −1 at 100th cycle). These results suggest that in addition to the chemical stability of the redox species, suppression of the solubility of active materials by intermolecular interactions is effective for improving cycle characteristics [ 51 , 52 , 53 , 54 , 55 ]. In this paper, we have designed and synthesized a novel TOT derivative 4 with three 4-pyridyl groups introduced at the 2-,6- and10-positions of the TOT skeleton, preserving the three-fold symmetry as the first ligand based on the TOT s for metal complexes ( Scheme 1 ).…”

Benzo[1,2,3]dithiazole Compounds: A History of Synthesis and Their Renewed Applicability in Materials and Synthetic Chemistry, Originating from the Herz Reaction

“…Besides the suggestion by Makarov et al that these titled [1,2,3]dithiazole structures could feature in photovoltaic materials due to their absorbance characteristics [11], there does not yet appear any further consideration described in the literature. To conclude this section, we note that Zhang and Tuttle have recently published a report into the use of these same compound series as organic electrode materials for a targeted end-use in batteries [117]. Their benzodithiazole-based solid retained 94% of its initial energy capacity after 400 charges/discharge cycles [117], further demonstrating the potential applicability of these conductive properties.…”

“…To conclude this section, we note that Zhang and Tuttle have recently published a report into the use of these same compound series as organic electrode materials for a targeted end-use in batteries [117]. Their benzodithiazole-based solid retained 94% of its initial energy capacity after 400 charges/discharge cycles [117], further demonstrating the potential applicability of these conductive properties.…”