π-Conjugated redox-active two-dimensional polymers as organic cathode materials

Jin, Zexin; Cheng, Qin; Evans, Austin M.; Gray, Jesse; Zhang, Ruiwen; Bao, Si Tong; Wei, Fengkai; Venkataraman, Latha; Yang, Yuan; Nuckolls, Colin

doi:10.1039/d1sc07157b

Cited by 18 publications

(19 citation statements)

References 28 publications

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“…The potential of 2DPs as energy storage materials has been substantially demonstrated (refs , , , , , , , , , , , , , , , , , , , , , , , , , , − ). However, the limited number of chemical reactions and redox-active monomers explored has limited a deeper exploration of energy storage applications in 2DPs.…”

Section: Properties and Applications Of Two-dimensional Polymersmentioning

confidence: 99%

Two-Dimensional Polymers and Polymerizations

et al. 2021

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Synthetic chemists have developed robust methods to synthesize discrete molecules, linear and branched polymers, and disordered cross-linked networks. However, two-dimensional polymers (2DPs) prepared from designed monomers have been long missing from these capabilities, both as objects of chemical synthesis and in nature. Recently, new polymerization strategies and characterization methods have enabled the unambiguous realization of covalently linked macromolecular sheets. Here we review 2DPs and 2D polymerization methods. Three predominant 2D polymerization strategies have emerged to date, which produce 2DPs either as monolayers or multilayer assemblies. We discuss the fundamental understanding and scope of each of these approaches, including: the bond-forming reactions used, the synthetic diversity of 2DPs prepared, their multilayer stacking behaviors, nanoscale and mesoscale structures, and macroscale morphologies. Additionally, we describe the analytical tools currently available to characterize 2DPs in their various isolated forms. Finally, we review emergent 2DP properties and the potential applications of planar macromolecules. Throughout, we highlight achievements in 2D polymerization and identify opportunities for continued study.

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Section: Properties and Applications Of Two-dimensional Polymersmentioning

confidence: 99%

Two-Dimensional Polymers and Polymerizations

et al. 2021

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“…Twistacenes and helicenes , (Figure a) are two main types of chiral, π-conjugated materials that have captivated considerable attention due to their extraordinary chiroptic properties. , Helicenes are conjugated, aromatic ribbons that coil around a cylindrical core and have found application in nonlinear optics, magnetochirality, spin filters, asymmetric catalysis, and photoswitches. , Twistacenes are conjugated ribbons with strain-induced contortion along the main molecular axis . We have developed a new type of helicene-containing, π-conjugated twistacene ribbonshelical perylene diimide , (hPDI, Figure b)that have excelled in applications such as batteries, , pseudocapacitors, , photovoltaics, , field effect transistors, an electron transport layer in perovskite solar cells, and photodetectors . However, until now, it has been difficult to control the handedness of these twistacenes.…”

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“…10,11 Twistacenes are conjugated ribbons with strain-induced contortion along the main molecular axis. 12 We have developed a new type of helicene-containing, π-conjugated twistacene ribbons�helical perylene diimide 13,14 (hPDI, Figure 1b)�that have excelled in applications such as batteries, 15,16 pseudocapacitors, 17,18 photovoltaics, 19,20 field effect transistors, 13 an electron transport layer in perovskite solar cells, 21 and photodetectors. 22 However, until now, it has been difficult to control the handedness of these twistacenes.…”

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Remote Control of Dynamic Twistacene Chirality

et al. 2022

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We report a reliable way to manipulate the dynamic, axial chirality in perylene diimide (PDI)-based twistacenes. Specifically, we reveal how chiral substituents on the imide position induce the helicity in a series of PDI-based twistacenes. We demonstrate that this remote chirality is able to control the helicity of flexible [4]helicene subunits by UV–vis, CD spectroscopy, X-ray crystallography, and TDDFT calculations. Furthermore, we have discovered that both the chiral substituent and the solvent each has a strong impact on the sign and intensity of the CD signals, highlighting the control of the dynamic helicity in this flexible system. DFT calculations suggest that the steric interaction of the chiral substituents is the important factor in how well a particular group is at inducing a preferred helicity.

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“…Furthermore, we demonstrated these molecular ladders have great potential as fast-charging and long-life OEMs. The most efficacious member of this series, hPDI [6], highlights four design principles for organic electrodes to achieve exceptional rate capability and cycling stability (Figure 1b): (1) redox-active PDI subunits that feature high stability and fast redox kinetics; 27,28 (2) insoluble macromolecules that overcome the dissolution issue associated with small molecules; (3) molecular contortion that facilitates lithium-ion transport and thus leads to high ionic diffusivity within the solid material; 29 and (4) a precisely defined fully conjugated ladder structure that provides high electrical conductivity.…”

Section: ■ Introductionmentioning

confidence: 99%

Iterative Synthesis of Contorted Macromolecular Ladders for Fast-Charging and Long-Life Lithium Batteries

et al. 2022

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We report here an iterative synthesis of long helical perylene diimide (hPDI[n]) nanoribbons with a length up to 16 fused benzene rings. These contorted, ladder-type conjugated, and atomically precise nanoribbons show great potential as organic fast-charging and long-lifetime battery cathodes. By tuning the length of the hPDI[n] oligomers, we can simultaneously modulate the electrical conductivity and ionic diffusivity of the material. The length of the ladders adjusts both the conjugation for electron transport and the contortion for lithium-ion transport. The longest oligomer, hPDI[6], when fabricated as the cathode in lithium batteries, features both high electrical conductivity and high ionic diffusivity. This electrode material exhibits a high power density and can be charged in less than 1 min to 66% of its maximum capacity. Remarkably, this material also has exceptional cycling stability and can operate for up to 10,000 charging–discharging cycles without any appreciable capacity decay. The design principles described here chart a clear path for organic battery electrodes that are sustainable, fast-charging, and long lasting.

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π-Conjugated redox-active two-dimensional polymers as organic cathode materials

Abstract: Redox-active two-dimensional polymers (RA-2DPs) are promising lithium battery organic cathode materials due to their regular porosities and high chemical stabilities.

Cited by 18 publications

References 28 publications

Two-Dimensional Polymers and Polymerizations

Two-Dimensional Polymers and Polymerizations

Remote Control of Dynamic Twistacene Chirality

Iterative Synthesis of Contorted Macromolecular Ladders for Fast-Charging and Long-Life Lithium Batteries

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