A carbonyl-rich covalent organic framework as a high-performance cathode material for aqueous rechargeable zinc-ion batteries

Ma, Dingxuan; Zhao, Huimin; Cao, Fan; Zhao, Huihui; Li, Jixin; Wang, Lei; Liu, Kang

doi:10.1039/d1sc06412f

Cited by 83 publications

(73 citation statements)

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“…In future work, we will alleviate the partial solubility of these materials by cross-linking or by incorporation into polymeric networks, 55,56,[61][62][63][64] which are common methods to overcome this problem in redox-active organic materials. One of the most exciting features of organic electrode materials is that they can be readily adapted to work with almost any cation, including those such as Na + and Mg 2+ that are more abundant than Li + , [65][66][67] and their redox properties can be optimized by tuning hard-soft acid-base interactions. [68][69][70] Indeed, previous molecular studies have demonstrated that 1,2-diones are promising potential electrode materials for Mg-ion batteries, because the two one-electron waves observed with monovalent cations such as Li + collapse into a single two-electron reduction wave with Mg 2+ cations due to the excellent hard-hard match of the divalent cation and the reduced carbonyl groups.…”

Section: Resultsmentioning

confidence: 99%

Unexpected Direct Synthesis of Tunable Redox-Active Benzil-Linked Polymers via the Benzoin Reaction

Cong

Kim

Gannett

et al. 2022

Preprint

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New strategies for the sustainable synthesis of redox-active organic polymers could lead to next-generation organic electrode materials for electrochemical energy storage, electrocatalysis, and electro-swing chemical separations. Among redox-active moieties, benzils or aromatic 1,2-diones are particularly attractive due to their high theoretical gravimetric capacities and fast charge/discharge rates. Herein, we demonstrate that the cyanide-catalyzed polymerization of simple dialdehyde mon-omers unexpectedly leads to insoluble redox-active benzil-linked polymers instead of the expected benzoin polymers, as confirmed by solid-state nuclear magnetic resonance spectroscopy and electrochemical characterization. Mechanistic stud-ies suggest that cyanide-mediated benzoin oxidation occurs by hydride transfer to the solvent, and that the insolubility of the benzil-linked polymers protects them from subsequent cyanolysis. The thiophene-based polymer poly(BTDA) is an in-triguing organic electrode material that demonstrates two reversible one-electron reductions with monovalent cations such as Li+ and Na+ but one two-electron reduction with divalent Mg2+. Furthermore, in lithium metal half cells, poly(BTDA) pos-seses an experimental capacity of 106 mAh/g and promising rate capabilities (64% capacity retention when the discharge rate is increased from 0.1 to 10 A/g). As such, the tandem benzoin-oxidation polymerization reported herein represents a sustainable method for the synthesis of highly tunable and redox-active organic materials.

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Section: Resultsmentioning

confidence: 99%

Unexpected Direct Synthesis of Tunable Redox-Active Benzil-Linked Polymers via the Benzoin Reaction

Cong

Kim

Gannett

et al. 2022

Preprint

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“…[ 3,22,23,44–49,120–130 ] Moreover, the emerging ion‐conducting COFs with excellent ionic conductivity and high cation transfer number can reduce the battery polarization and improve the charging/discharging kinetics of electrodes. [ 131–143 ] The distinctive directional selectivity of ionic conduction in COFs is obviously different from the typical inorganic solid conductors and polymer conductors, so that COFs are suitable for diverse battery applications, including lithium‐ion, [ 144–166 ] lithium–sulfur, [ 167–208 ] sodium‐ion, [ 209–214 ] potassium‐ion, [ 215–219 ] lithium–CO 2 , [ 220–223 ] zinc‐ion, [ 224–230 ] zinc–air batteries, [ 231–234 ] etc. In this section, the traditional classification method of battery types is replaced by the classification according to the components among the dif...…”

Section: Applications Of Ion‐conducting Cof In Rechargeable Batteriesmentioning

confidence: 99%

Covalent Organic Framework for Rechargeable Batteries: Mechanisms and Properties of Ionic Conduction

Cao

Wang

et al. 2022

Advanced Energy Materials

102

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The ionic conduction plays an important role in the charging/discharging kinetics in rechargeable batteries, mainly including the steps of diffusion in the electrodes, transport in the electrolytes, and permeation through the electrode/electrolyte interphases. [8][9][10] Generally, the ionic transport is a critical control step in the electrochemical reactions, because it is much slower kinetics than electron transport. [8,11] Thus, regulating the ion-transport behavior is very vital to achieve fast-charging secondary batteries. [6,12] Mechanism exploration and novel material design become two important strategies to tackle the sluggish ionconduction kinetics. [13][14][15][16][17] In the secondary battery, the environment of ionic conduction can be roughly divided into liquid electrolytes and solid conductors. The ionic diffusion in the liquid electrolytes can be very fast. However, the flammability of organic solvents and the instability of salts (such as LiPF 6 ) at elevated temperature limit its commercial application. [18,19] The solid conductor is a safer choice to replace the current liquid electrolyte, but still suffers a serious impediment of low ionic conductivity. [20,21] Recently, covalent organic frameworks (COFs), an emerging type of crystalline porous materials, are considered to be a potential solid conductor. [22,23] Depending on the topological establishment of building blocks, COFs are classified into 2D COFs and 3D COFs. Unless otherwise noted, the COFs in this review specifically refer to 2D COFs. 2D COFs typically crystallize as stacked sheets through the π-π interaction between adjacent monolayers, meanwhile the organic units are connected by the covalent bond to form reticular framework with periodic channel structure. [24][25][26][27] Based on the nature of synthetic reactions, COFs have been synthesized with boroxine, boronate ester, borosilicate, triazine, imine, hydrazone, borazine, imide, spiroborate, amide linkages, etc. [24,25] In addition, based on the symmetry of the monomers, COFs can be designed in various topologies, such as tetragonal, hexagonal, rhombic, and trigonal. [24,25] Over the recent decades, a variety of synthetic approaches have been developed to prepare COFs, such as solvothermal synthesis, microwave synthesis, ionothermal synthesis, mechanochemical synthesis, and interfacial synthesis. [24,25] Among them, the solvothermal synthesis under a sealed vessel with a suitable temperature can produce highly crystalline COFs, but this method always needs a long Ionic conduction plays a critical role in the process of electrode reactions and the charge transfer kinetics in a rechargeable battery. Covalent organic frameworks (COFs) have emerged as an exciting new class of ionic conductors, and have made great progress in terms of their application in rechargeable batteries. The unique features of COFs, such as well-defined directional channels, functional diversity, and structural robustness, endow COF-based conductors with a low ionic diffusion energy barrier and excellent t...

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“…[24][25][26][27][28][29][30][31] It is well-known that the high surface area is conductive to embed Li + ions into deep pore sites and enhance their shuttle velocity in the pore. 32,33 Besides, COFs also exhibit better stability than traditional organic materials and hardly dissolve in most solvents. 34 Zhao et al 35 explored the few-layer TP-COF in LIBs by using mechanical exfoliation, where the asexfoliated TP-COF could enable the reversible reaction of Li + with C═N and C═O, and deliver a high initial capacity of 110 mAh/g.…”

Section: Introductionmentioning

confidence: 99%

Covalent organic framework containing dual redox centers as an efficient anode in Li‐ion batteries

et al. 2022

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Covalent organic frameworks (COFs) with periodic channels and tunable chemical structures have been widely considered as promising electrode materials in rechargeable batteries. However, the design and construction of high-performance COFs-based electrodes still face some challenges in the introduction of multiple efficient redox centers as well as the reduction of dead mass. To address these issues, a unique COF containing double active centers (C═N and N═N) is developed as an anode in rechargeable lithium-ion batteries (LIBs). The as-prepared COF displays excellent electrochemical performance due to its remarkable structural stability and the existence of many active groups. Meanwhile, its electrochemical performance is significantly better than that of the small molecule compound or the linear polymer with the same construction units. Even at a high current density of 5 A/g, the LIBs with COF electrodes remain at a high discharge capacity of 227 mAh/g after 2000 cycles. Moreover, the distinction in electrochemical performances of these three materials is further revealed by calculation. This study illustrates the importance of molecular structure design for improving the performance of organic electrodes.

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A carbonyl-rich covalent organic framework as a high-performance cathode material for aqueous rechargeable zinc-ion batteries

Abstract: A covalent organic framework (Tp-PTO-COF) with carbonyl active sites was proposed as a novel cathode material and successfully applied in aqueous rechargeable zinc-ion batteries (ZIBs).

Cited by 83 publications

References 50 publications

Unexpected Direct Synthesis of Tunable Redox-Active Benzil-Linked Polymers via the Benzoin Reaction

Unexpected Direct Synthesis of Tunable Redox-Active Benzil-Linked Polymers via the Benzoin Reaction

Covalent Organic Framework for Rechargeable Batteries: Mechanisms and Properties of Ionic Conduction

Covalent organic framework containing dual redox centers as an efficient anode in Li‐ion batteries

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