Amphiphilic Carborane-Based Covalent Organic Frameworks as Efficient Polysulfide Nano-Trappers for Lithium–Sulfur Batteries

Zhu, Yuejin; Yang, Jingying; Qiu, Xiaoyan; Li, Mingming; He, Guangke; Xie, Zhiying; Li, Xin; Yu, Haizhou

doi:10.1021/acsami.1c19705

Cited by 30 publications

(27 citation statements)

References 46 publications

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“…It is interesting to see the improved rate performance of the polysulfur-anchored S-DUT-177 in comparison to most of the sulfur-impregnated porous COFs (Table S9). ,− Since the sulfur loading was possible only up to 0.55 mg/cm 2 in the S-DUT-177-derived electrode owing to the very low density of the material, the areal capacity (1.8 mA h/cm 2 @0.25 mA/cm 2 ) is comparatively low. Also, in our derived electrode, the organic backbone contributes considerably to the weight along with the sulfur content.…”

Section: Resultsmentioning

confidence: 99%

Porous Dithiine-Linked Covalent Organic Framework as a Dynamic Platform for Covalent Polysulfide Anchoring in Lithium–Sulfur Battery Cathodes

et al. 2022

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Dithiine linkage formation via a dynamic and self-correcting nucleophilic aromatic substitution reaction enables the de novo synthesis of a porous thianthrene-based two-dimensional covalent organic framework (COF). For the first time, this organo-sulfur moiety is integrated as a structural building block into a crystalline layered COF. The structure of the new material deviates from the typical planar interlayer π-stacking of the COF to form undulated layers caused by bending along the C–S–C bridge, without loss of aromaticity and crystallinity of the overall COF structure. Comprehensive experimental and theoretical investigations of the COF and a model compound, featuring the thianthrene moiety, suggest partial delocalization of sulfur lone pair electrons over the aromatic backbone of the COF decreasing the band gap and promoting redox activity. Postsynthetic sulfurization allows for direct covalent attachment of polysulfides to the carbon backbone of the framework to afford a molecular-designed cathode material for lithium–sulfur (Li–S) batteries with a minimized polysulfide shuttle. The fabricated coin cell delivers nearly 77% of the initial capacity even after 500 charge–discharge cycles at 500 mA/g current density. This novel sulfur linkage in COF chemistry is an ideal structural motif for designing model materials for studying advanced electrode materials for Li–S batteries on a molecular level.

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Section: Resultsmentioning

confidence: 99%

Porous Dithiine-Linked Covalent Organic Framework as a Dynamic Platform for Covalent Polysulfide Anchoring in Lithium–Sulfur Battery Cathodes

et al. 2022

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“…This feature is favorable to accelerating Li + transportation, reducing polarization, and improving rate performance. [ 2a,5,13 ]…”

Section: Resultsmentioning

confidence: 99%

A Facile Immobilization Strategy for Soluble Phosphazene to Actualize Stable and Safe Lithium–Sulfur Batteries

Zhu

Chen

Liu

et al. 2022

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Lithium–sulfur batteries (LSBs) have attracted extensive attention owing to their high energy density and abundant sulfur resources. However, LSBs are still restricted by the unsatisfactory electrochemical performance resulting from the shuttle effect of lithium polysulfide (LiPSs), and the potential fire hazard caused by inflammable ether electrolytes and polyolefin separators. Herein, a facile immobilization strategy for hexachlorocyclotriphosphazene (HCCP) is creatively applied to address the above issues simultaneously. Insoluble HCCP cross‐linked microspheres (H‐CMP) are firstly obtained at ambient temperature using tannic acid (TA) as a cross‐linking agent and then a multifunctional separator coating is constructed based on H‐CMP. The released phosphorus‐related radicals from H‐CMP in wide temperatures effectively prevent the combustion of electrolytes and separators, and hence improve the fire safety of the Li–S pouch cell. Furthermore, H‐CMP availably chemisorbs LiPSs to interdict the shuttle effect, thereby dramatically improving the electrochemical performance of LSBs. The effectiveness of this strategy is also verified in high sulfur loading (6.38 mg cm‐2), high temperature (50 °C), and Li–S pouch cells. More importantly, H‐CMP exhibits sufficient stability for Li metal and suppression of Li dendrites. This facile immobilization strategy for multifunctional phosphazenes provides a competitive option for the large‐scale fabrication of high‐safety and high‐performance LSBs.

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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

114

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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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Amphiphilic Carborane-Based Covalent Organic Frameworks as Efficient Polysulfide Nano-Trappers for Lithium–Sulfur Batteries

Cited by 30 publications

References 46 publications

Porous Dithiine-Linked Covalent Organic Framework as a Dynamic Platform for Covalent Polysulfide Anchoring in Lithium–Sulfur Battery Cathodes

Porous Dithiine-Linked Covalent Organic Framework as a Dynamic Platform for Covalent Polysulfide Anchoring in Lithium–Sulfur Battery Cathodes

A Facile Immobilization Strategy for Soluble Phosphazene to Actualize Stable and Safe Lithium–Sulfur Batteries

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

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