Poly(vinyldibenzothiophenesulfone): Its Redox Capability at Very Negative Potential Toward an All‐Organic Rechargeable Device with High‐Energy Density

Abstract

Dibenzothiophenesulfone undergoes a two‐electron reduction in a single step at a very negative potential of −1.8 V (versus Ag/AgCl) in organic electrolytes, due to the electron‐withdrawing sulfone group and the stability of the resulting dianion. The heterogeneous electron‐transfer rate constant for the reduction is approximately 10−1 cm s−1, which is significantly faster than most redox‐active species. The results presented herein suggest that dibenzothiophenesulfone is a potential candidate for use as an anode‐active material with high‐energy density. In addition, radical polymerization of vinyldibenzothiophenesulfone yielded poly(vinyldibenzothiophenesulfone) with a high molecular weight. A rechargeable device is fabricated with only organic compounds; poly(vinyldibenzothiophenesulfone) as the anode, 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO)‐substituted poly(methacrylate) as the cathode, and tetraethylammonium salt and organic solvent as the electrolyte. This device yields a maximum output voltage of 2.6 V in these organic devices, and the active component of the anode displays a very high‐energy density of >500 mWh g−1.

Reversible Hydrogen Releasing and Fixing with Poly(Vinylfluorenol) through a Mild Ir‐Catalyzed Dehydrogenation and Electrochemical Hydrogenation

“…The chronoamperogram of the poly(vinylfluorenone) layer on the carbon plate gave linear Cottrell plots of the current versus t −1/2 in the early stage of electrolysis under semi‐infinite diffusion, supporting diffusion‐limited behavior, and the diffusion coefficient can be obtained from the slope of plots ( Figure ). The charge diffusion coefficient ( D ) was 7.2 × 10 −12 cm 2 s −1 and was on the same order as those previously reported for redox polymers suitable for facile charge storage, suggesting the swift electron‐transport characteristics of the poly(vinylfluorenone) layer resulting from its high population of fluorenone units and swellable amorphous polymer layers.…”

Through-Space Electronic Conjugation Enhances Co-Electrocatalytic Reduction of CO2 to CO by a Molecular Cr Complex

“…[21][22][23][24] Intrigued by the notion that TSEC could enhance catalytic activity by generating co-catalyst assemblies, we sought to identify a suitable RM and transition metal complex. We selected dibenzothiophene-5,5dioxide (DBTD) as the RM (Figure 1), which is derived from a petroleum contaminant 25 and has welldefined electrochemical properties at reducing potentials, 26 to pair with a Cr-based catalyst developed in our lab, Cr( tbu dhbpy)Cl(H2O) (Figure 1). [27][28] Herein, we report to our knowledge the only example where TSEC has been used to develop a homogeneous co-electrocatalytic system.…”

Recent Progress in Multivalent Metal (Mg, Zn, Ca, and Al) and Metal‐Ion Rechargeable Batteries with Organic Materials as Promising Electrodes

“…To gain insight into these issues, effective approaches are encouraged to be proposed to improve the current situation of organic‐electrode‐based multivalent metal and metal‐ion batteries. Actually, recent successful strategies from organic lithium (Li)‐ion batteries based on conductive polymers, conjugated polymers, carbonyl compounds,[37a,41‐48] and new redox chemistry compounds afford us sufficient experiences that merit attention. Innovative demonstrations including all‐organic‐electrode and all‐solid‐state batteries have also been realized based on these materials .…”

“…Actually, recent successful strategies from organic lithium (Li)‐ion batteries based on conductive polymers, conjugated polymers, carbonyl compounds,[37a,41‐48] and new redox chemistry compounds afford us sufficient experiences that merit attention. Innovative demonstrations including all‐organic‐electrode and all‐solid‐state batteries have also been realized based on these materials . Moreover, due to the distinct superiorities including enlarged surface area, enhanced electrochemical reactivity, and shortened pathway for charge transfer that could be provided by nanostructures, valuable experience from Li‐ion batteries on organic nanostructures (e.g., conductive polymers, conjugated polymers, and covalent organic frameworks) could provide opportunities for organic multivalent batteries to achieve improved electrochemical performance.…”