Poly(DCAQI): Synthesis and characterization of a new redox-active polymer

Abstract

Redox-active anthraquinone based polymers are synthesized by the introduction of a polymerizable vinyl and ethynyl group, respectively, resulting in redox-active monomers, which electrochemical behaviors are tailored by the modification of the keto groups to N-cyanoimine moieties. These monomers can be polymerized by free radical polymerization and Rh-catalyzed polymerization methods, respectively. The resulting polymers are obtained in molar masses (M n ) of 4,400 to 16,800 g mol 21 as well as high yields of up to 97%.The monomers and polymers are furthermore electrochemically characterized by cyclic voltammetry. The monomers exhibit two one-electron redox reactions at about 20.6 and 21.0 V versus Fc 1 /Fc. The N-cyanoimine units are, however, partially hydrolyzed during the polymerization step or during the electrochemical measurements and degenerate to carbonyl groups, resulting in a new reduction signal at 21.26 V versus Fc

Polymeric Active Materials for Redox Flow Battery Application

“…(a) Reported redox-active polymers for flow battery applications. ,,, (b) Cycling test of BODIPY-based PRFB. The upper figure is the static cell of poly­(TEMPO -co- PEGMA) and poly­(TEMPO).…”

“…Other Polymeric Materials for Nonaqueous RFB. Several other redox-active polymers, including dicyanoanthraquinone diimine containing polymer (poly(DCAQI)), 104 phthalimide-containing polymer, 105 cyclopropenium-containing polymer, 106 poly(para-nitrostyrene), 107 and boron-dipyrromethene (BODIPY)-based polymers, 108 have been reported as redox-active materials in nonaqueous RFB, and some were tested in static cells. The structures of those polymers are summarized in Figure 8a.…”

Design Strategies for Promising Organic Positive Electrodes in Lithium-Ion Batteries: Quinones and Carbon Materials

“…Recently, the functionalization strategy based on the incorporation of target functional groups into organic materials has been extensively studied for its potential to deliver rationally designed organic materials for utilization as positive electrodes in lithium-ion batteries. ,,,,− Redox-active quinones with carbonyl moieties have been suggested in a variety of studies, not only for lithium-ion batteries but also for other electrochemical energy storage systems. ,,,,− In fact, these studies have examined a broad range of quinone derivatives dissolved in various electrolytes as potential redox-active components in redox flow batteries. − Aspuru-Guzik and co-workers employed a high-throughput computational screening approach to study the redox potentials of a selected set of quinones and hydroquinones, including the promising classes of 9,10-anthraquinones, 1,2-benzoquinones, 2,3-naphthoquinones, and 2,3-anthraquinones, for both anolytes and catholytes in redox flow batteries . Assary and co-workers studied the redox properties of 50 anthraquinone derivatives to evaluate their potential as anolytes in redox flow batteries .…”

Impact of Backbone Tether Length and Structure on the Electrochemical Performance of Viologen Redox Active Polymers

“…3,4 Redox active polymers (RAPs) based on organic moieties offer exceptional chemical and structural versatility as redox couples for NRFBs. [5][6][7][8]62,63 Recently, our groups reported on the use of a highly soluble viologen polymer 1 (Figure 1) as a charge storage medium for use in a new type of size exclusion NRFB. 9 This strategy solves issues with the lack of high-performance membranes for nonaqueous electrolytes and minimizes species crossover between compartments.…”

“…With the impetus of sustainable energy technologies such as wind and solar, there is a demand for efficient electrical energy storage devices that couple to these intermittent sources. Nonaqueous flow batteries (NRFBs) are attractive candidates for grid energy storage that address issues related to energy density and load leveling. , These devices store charge in solution by utilizing high energy density redox couples, that is, an anolyte and a catholyte, which are retained in separate compartments and flown through an electrode assembly. , Redox active polymers (RAPs) based on organic moieties offer exceptional chemical and structural versatility as redox couples for NRFBs. − ,, Recently, our groups reported on the use of a highly soluble viologen polymer 1 (Figure ) as a charge storage medium for use in a new type of size exclusion NRFB . This strategy solves issues with the lack of high-performance membranes for nonaqueous electrolytes and minimizes species crossover between compartments.…”