Branched Poly(ethylene glycol)-Functionalized Covalent Organic Frameworks as Solid Electrolytes

Wang, Yuxiang; Zhang, Kun; Jiang, Xinzhu; Liu, Ziya; Bian, Shuyang; Pan, Yaoyao; Shan, Zhen; Wu, Miaomiao; Xu, Bingqing; Zhang, Gen

doi:10.1021/acsaem.1c02426

Cited by 20 publications

(20 citation statements)

References 31 publications

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“…As a result, the material containing highest density accumulation of PEO (COF-PEO-9-Li) exhibited the superior ionic conductivity over 10 −3 S/cm at 200°C. The similar trend was also demonstrated by branched PEO-functionalized COFs as solid conductors [26]. Recently, Horike used the similar side-chain engineering strategy to fabricate a gel-state COF (COF-Gel) with facile processability by implanting soft branched alkyl chains as internal plasticizers into the nanopores of COFs (Figure 2c) [25].…”

Section: Cofs For Lithium-ion Conductionsupporting

confidence: 57%

Covalent Organic Frameworks for Ion Conduction

Lü¹,

Gao²

2023

Covalent Organic Frameworks

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Covalent organic frameworks (COFs) are an emerging class of crystalline porous materials constructed by the precise reticulation of organic building blocks through dynamic covalent bonds. Due to their facile preparation, easy modulation and functionalization, COFs have been considered as a powerful platform for engineering molecular devices in various fields, such as catalysis, energy storage and conversion, sensing, and bioengineering. Particularly, the highly ordered pores in the backbones with controlled pore size, topology, and interface property provide ideal pathways for the long-term ion conduction. Herein, we summarized the latest progress of COFs as solid ion conductors in energy devices, especially lithium-based batteries and fuel cells. The design strategies and performance in terms of transporting lithium ions, protons, and hydroxide anions are systematically illustrated. Finally, the current challenges and future research directions on COFs in energy devices are proposed, laying the groundwork for greater achievements for this emerging material.

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Section: Cofs For Lithium-ion Conductionsupporting

confidence: 57%

Covalent Organic Frameworks for Ion Conduction

Lü¹,

Gao²

2023

Covalent Organic Frameworks

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“…TFSI À ) and the crowded space in the channels for blocking the anion movement and facilitating Li + transport. [22] We also note that crystalline Cyano-OCF-EO exhibits a little bit higher electronic and ionic con-ductivity in comparison with amorphous Cyano-OCP-EO. This confirms the additional promotional role of crystalline engineering toward both ion and electron conduction.…”

Section: Angewandte Chemiementioning

confidence: 65%

Unique Octupolar 2D‐Polymer Frameworks as Mixed Conductors and Metal‐Free Catalysts for Dual‐Promoted Li and S Electrochemistry: Multi‐regulation Role of Ethoxylation Chemistry

Liu,

Mo,

Zhong

et al. 2023

Angew Chem Int Ed

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Here, we for the first time introduce ethoxylation chemistry to develop a new octupolar cyano‐vinylene‐linked 2D polymer framework (Cyano‐OCF‐EO) capable of acting as efficient mixed electron/ion conductors and metal‐free sulfur evolution catalysts for dual‐promoted Li and S electrochemistry. Our strategy creates a unique interconnected network of strongly‐coupled donor 3‐(acceptor‐core) octupoles in Cyano‐OCF‐EO, affording enhanced intramolecular charge transfer, substantial active sites and crowded open channels. This enables Cyano‐OCF‐EO as a new versatile separator modifier, which endows the modified separator with superior catalytic activity for sulfur conversion and rapid Li ion conduction with the high Li+ transference number up to 0.94. Thus, the incorporation of Cyano‐OCF‐EO can concurrently regulate sulfur redox reactions and Li‐ion flux in Li−S cells, attaining boosted bidirectional redox kinetics, inhibited polysulfide shuttle and dendrite‐free Li anodes. The Cyano‐OCF‐EO‐involved Li−S cell is endowed with excellent overall electrochemical performance especially large areal capacity of 7.5 mAh cm−2 at high sulfur loading of 8.7 mg cm−2. Mechanistic studies unveil the dominant multi‐promoting effect of the triethoxylation on electron and ion conduction, polysulfide adsorption and catalytic conversion as well as previously‐unexplored −CN/C−O dual‐site synergistic effect for enhanced polysulfide adsorption and reduced energy barrier toward Li2S conversion.

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“…Functionalized 2D COFs having PEO/PEG units directly attached to their framework structure are innovative materials, which bridge benefits of COFs and the polymer host used in conventional PEs. [205][206][207][208] These polymer units can influence the crystallinity of COFs and are often suitable for improving the thermal and mechanical properties of nonfunctionalized 2D COFs. In this regard, Zhang et al introduced PEO into the inner space of a 2D COF by self-assembly approach to prepare glassy COF electrolytes (Figure 36).…”

Section: Cofs: Organic Nanofillers For Pocesmentioning

confidence: 99%

“…Later, there have been attempts to introduce various branched PEO chains onto the pores of COF by condensing 1,3,5‐tris(4‐formyl‐phenyl)‐benzene with three PEG‐based hydrazide monomers. [ 207 ] LiTFSI was introduced into the COF through a soaking process to obtain COF‐PEG‐Bn‐Li (Figure 36, Bn represents no. of chains with n = 1,3,6).…”

Section: Cofs: Organic Nanofillers For Pocesmentioning

confidence: 99%

2D Layered Nanomaterials as Fillers in Polymer Composite Electrolytes for Lithium Batteries

Vijayakumar

Ghosh

Asokan

et al. 2023

Advanced Energy Materials

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there have been tremendous efforts to improve their performance, safety, costeffectiveness, and sustainability. [1] In the last four decades, dedicated research in material science toward developing electrodes, separators, electrolytes, current collectors, packaging materials, etc., have significantly contributed to the advancement of LIB technology. [2] Indeed, the progress in cell engineering and processing conditions has aided the evolution of high energy density LIBs (energy density >250 Wh kg −1 ), leading to their widespread application spanning from electronic devices to electric vehicles and stationary/ grid energy storage. [1] Considering the contributions that led to the invention of LIB technology, John B. Goodenough, Stanley Whittingham, and Akira Yoshino received the Chemistry Nobel Prize in 2019. [3] Despite their huge success, research and development on LIBs and allied battery technologies are still a hot topic in both academia and industry offering opportunities for breakthrough innovations and discoveries. Figure 1a presents a schematic illustration of the state-of-theart LIB and its main components. Liquid electrolytes based on organic solvents and lithium salts are the primary choice as electrolytes in LIBs due to their high ionic conductivity and good Polymer composite electrolytes (PCEs), i.e., materials combining the disciplines of polymer chemistry, inorganic chemistry, and electrochemistry, have received tremendous attention within academia and industry for lithiumbased battery applications. While PCEs often comprise 3D micro-or nanoparticles, this review thoroughly summarizes the prospects of 2D layered inorganic, organic, and hybrid nanomaterials as active (ion conductive) or passive (nonion conductive) fillers in PCEs. The synthetic inorganic nanofillers covered here include graphene oxide, boron nitride, transition metal chalcogenides, phosphorene, and MXenes. Furthermore, the use of naturally occurring 2D layered clay minerals, such as layered double hydroxides and silicates, in PCEs is also thoroughly detailed considering their impact on battery cell performance. Despite the dominance of 2D layered inorganic materials, their organic and hybrid counterparts, such as 2D covalent organic frameworks and 2D metal-organic frameworks are also identified as tuneable nanofillers for use in PCE. Hence, this review gives an overview of the plethora of options available for the selective development of both the 2D layered nanofillers and resulting PCEs, which can revolutionize the field of polymer-based solid-state electrolytes and their implementation in lithium and post-lithium batteries.

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Branched Poly(ethylene glycol)-Functionalized Covalent Organic Frameworks as Solid Electrolytes

Cited by 20 publications

References 31 publications

Covalent Organic Frameworks for Ion Conduction

Covalent Organic Frameworks for Ion Conduction

Unique Octupolar 2D‐Polymer Frameworks as Mixed Conductors and Metal‐Free Catalysts for Dual‐Promoted Li and S Electrochemistry: Multi‐regulation Role of Ethoxylation Chemistry

2D Layered Nanomaterials as Fillers in Polymer Composite Electrolytes for Lithium Batteries

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