Donor–Node–Acceptor Polymer with Excellent n-Doped State for High-Performance Ambipolar Flexible Supercapacitors

Abstract

A redox active polymer network film containing donor–node–acceptor (D–n–A) units was prepared by using the electropolymerization (EP) of the precursor (4Cz–4Cl–PBI). The polymer film was characterized by the UV–vis absorption, FT-IR, SEM, XRD and electrochemical techniques. The precursor contains phenyl connected two carbazoles (D) linked by the two sp3 N-nodes on both sides of a tetrachloro-substituted PBI (A). The two N-nodes block the conjugation between D and A units, resulting in an independent redox activity (from D and A) and doping behaviors. This novel concept of the D–n–A polymer effectively increases the conductivity and stability of the n-doped state. The EP film can be prepared on ITO and flexible electrodes with large area, smooth surface morphology, controllable thickness, and nanoporous structure. Notably, the polymer network film showed ambipolar doping characteristics, with high capacitance (both n- and p-doped states). These properties are very suitable to construct ambipolar electrodes for the flexible supercapacitors. The flexible solid-state supercapacitor devices made from poly­(4Cz–4Cl–PBI) network film can readily charge and discharge (fast electron transfer). The flexible supercapacitor showed a very large potential window (2.2 V) and high power density (17.4 W cm–3).

In-situ electropolymerized bipolar organic cathode for stable and high-rate lithium-ion batteries

“…These characteristic peaks confirm the co-existence of carbonyl groups and two types of C-N bonds in APCNDI. The 13 C NMR spectrum shows characteristic chemical shifts at 162 and 141 ppm corresponding to the C atoms in the carbonyl groups of NTCDI and in the C-N bonds of the carbazole groups [39]. The absorption peaks in the UV-vis spectra are consistent with the results reported in the Ref.…”

“…3d). A peak at 745 cm −1 was observed in the FTIR spectra of the pristine and low-voltage-cycled cathodes, which corresponds to the out-of-plane -C-H bending vibration of bis-substituted benzene [39]. Nevertheless, it is absent for the high-voltage cycled cathodes, showing that the benzene rings in the carbazole groups varied from bis-substituted to tri-substituted, confirming the occurrence of electropolymerization at high voltages.…”

Ambipolar PEDOT-Pendant Tetrachlorinated Perylene Diimide for Symmetric Supercapacitors

“…c) Comparison of ambipolar polymer cycling stability in positive (black) and negative (red) regions. 24,27 result of the interaction of densely packed PDI units in reduced states with cations. 42 In the negative region, the x-axis of the Nyquist plot shifts to more positive values, suggesting increased resistance relative to the positive and neutral potentials.…”

“…Qin et al synthesized a donor-nodeacceptor polymer, consisting of a dicarbazole donor unit and a tetrachlorinated perylene diimide (PDI) acceptor unit. 27 This donor-node-acceptor architecture decouples the performance of the positive and negative charge storage by separating the negative charge accepting PDI unit from the positive charge accepting dicarbazole through the node-like nitrogen atoms. 28 Contrary to most ambipolar polymers, the donor-nodeacceptor network polymer synthesized by Qin et al demonstrated remarkable negative region stability of 89% capacity retention after 1000 cycles, but limited positive region stability.…”

Electrochromism in Electropolymerized Films of Pyrene-Triphenylamine Derivatives

“…This decreases the experimental time and cost and partially solves the solubility problem of some compounds. A large number of electropolymerized films have been prepared from monomers functionalized with thiophene or carbazole derivatives [22,23,24,25,26,27,28]. In addition, triphenylamine groups have been used as polymerizable units to prepare thin films of organic and metal complexes by electropolymerization [29,30,31,32].…”