A Redox‐Active 2D Metal–Organic Framework for Efficient Lithium Storage with Extraordinary High Capacity

Jiang, Qiang; Xiong, Peixun; Liu, Jingjuan; Xie, Zhen; Wang, Qin‐Chao; Yang, Xiao‐Qing; Hu, Enyuan; Cao, Yuliang; Sun, Jie; Xu, Yunhua; Чэн, Лонг

doi:10.1002/anie.201914395

Cited by 195 publications

(197 citation statements)

References 28 publications

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“…Metal–organic frameworks (MOFs) with Zn 2+ and Fe 3+ as the metal nodes and organic carboxylates as the ligands were attempted for lithium‐ion batteries (LIBs) and SIBs, but the metal–organic ligand bonds were not strong enough to ensure redox reactions, and instead they broke to work via typical conversion reactions [15–17] . Recently, Bao's group reported two‐dimensional (2D) metal–hexaaminobenzene frameworks, which presented high pseudocapacitance based on the redox of the benzoid amine species [18, 19] .…”

Section: Figurementioning

confidence: 99%

A Two‐Dimensional Metal–Organic Polymer Enabled by Robust Nickel–Nitrogen and Hydrogen Bonds for Exceptional Sodium‐Ion Storage

et al. 2020

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Organic electrode materials suffer from low electronic conductivity and poor structure stability.H erein, ametal-organic polymer,Ni-coordinated tetramino-benzoquinone (Ni-TABQ), is synthesized via d-p hybridization. The polymer chains are stitched by hydrogen bonds to feature as arobust two-dimensional (2D) layered structure.Itoffers both electron conduction and Na + diffusion pathwaysa long the directions of the polymer chains and the hydrogen bonds.With both the conjugated benzoidcarbonyls and imines as the redox centers for the insertion and extraction of Na + ,t he Ni-TABQ delivers high capacities of about 469.5 mAh g À1 at 100 mA g À1 and 345.4 mAh g À1 at 8Ag À1 .The large capacities are sustained for 100 cycles with almost 100 %c oulombic efficiencies.T he exceptional electrochemical performance is attributed to the unique 2D electron conduction and Na + diffusion pathways enabled by the robust Ni-N and hydrogen bonds.

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Section: Figurementioning

confidence: 99%

A Two‐Dimensional Metal–Organic Polymer Enabled by Robust Nickel–Nitrogen and Hydrogen Bonds for Exceptional Sodium‐Ion Storage

et al. 2020

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“…Such performance can be further improved by innovations of ligand molecular structure. Additionally, Chen et al [79] . have reported a redox‐active 2D copper benzoquinoid (Cu‐THQ) MOF by a facile solvothermal method.…”

Section: Applications Of Mofs In Li‐ion Batteriesmentioning

confidence: 99%

“…Recently, other MOFs and ligands, such as Li-Co-MOFs, [78] 2D Cu-THQ MOF, [79] MIL-88B(Fe), [80] Cu 3 (HHTP) 2 , [81] Fe-MIL-88B, [82] and M-IOHCs, [83] are reported as cathodes for LIBs. For instance, Chen et al [81] have successfully synthesized a novel Cu 3 (HHTP) 2 material as cathode for LIBs.…”

Section: Mofs As Cathode Materials For Libsmentioning

confidence: 99%

“…Such performance can be further improved by innovations of ligand molecular structure. Additionally, Chen et al [79] have reported a redoxactive 2D copper benzoquinoid (Cu-THQ) MOF by a facile solvothermal method. The rationally designed electrode exhibits a reversible capacity of 387 mAh g À 1 , high energy density of 775 Wh kg À 1 and long cycle life.…”

Section: Mofs As Cathode Materials For Libsmentioning

confidence: 99%

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Progress and Perspective of Metal‐ and Covalent‐Organic Frameworks and their Derivatives for Lithium‐Ion Batteries

Cui

Dong

Chen

et al. 2020

Batteries & Supercaps

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Metal–organic frameworks (MOFs) or covalent–organic frameworks (COFs) have gained increasing attentions due to their high surface area, tunable structure, highly ordered pores and functional composition. Besides their applications in gas adsorption and separation, hydrogen storage, optics, magnetism and drug delivery, they have been widely employed as cathodes, anodes and separators for the research and development in lithium‐ion batteries (LIBs) due to the tunable structure, multi‐electron transfer, short pathway, and robust structural stability, etc. This review summarizes the general applied strategies and cases of MOF, COF and their composites as well as derivatives in LIBs. Compared to inorganic materials, the advantages of MOF/COF materials have made it possible to witness various successful cases with enhanced electrochemical performances. Moreover, this review provides some guidance for the controllable preparation and modification of MOF‐ and COF‐derived nanostructures through molecular engineering, rational design, and doping, as well as functional group modifications. In addition, we highlight timely progresses of the application of organic frameworks in LIBs, and also summarize many strategies of MOF/COF materials and their derivatives on enhancing the energy density, diffusion coefficient, rate performance and cycling stability for next‐generation LIBs with attractive features of high energy density, good rate performance, and superior cyclability.

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“…In these layered MOFs, each individual layer couples with the adjacent layers through hydrogen or van der Waals (vdW) forces . In comparison to traditional bulk MOFs, layered MOFs offer unique advantages in reaching much larger surface to volume ratios and high surface reactivity/sensitivity . In particular, layered MOFs involving transition‐metal cations are interesting owing to their partially filled orbitals with unique magnetic properties .…”

Section: Figurementioning

confidence: 99%

Achieving Morphological Control over Lamellar Manganese Metal‐Organic Framework through Modulated Bi‐Phase Growth

Shen

Shan

2020

Angewandte Chemie

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A modulated bi-phase synthesis towards large-scale manganese 1,4-benzenedicarboxylate (MnBDC) MOFs with a precise control over their morphology (bulk vs. layered) is presented. Metal precursors and organic ligands are separated to reduce the kinetic reaction rates for better control over the crystallization process. Based on scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), and Raman spectroscopy studies, the continuous ligand supply along with the presence of pyridine capping agent are highly effective in promoting the layer-bylayer growth and achieving large crystal sizes. Once layered MnBDC is stabilized, topotactic intercalation chemistry was used to demonstrate the feasibility of bromine intercalation on these layered materials. Bromine intercalation is possible between the MOFs layers for the first time. Bromine intercalation causes colossal reduction in layered MnBDC band gap while it has no observable effect on bulk MOFs.The structure and morphology of metal-organic frameworks (MOFs) play a key factor in determining their practical applications and functionalities ranging from gas separation to catalytic energy conversion and to sensing. Layered MOFs are a subcategory of MOFs in which metal clusters and organic ligands are connected through the coordination bonding which tiles up in two dimensions. In these layered MOFs, each individual layer couples with the adjacent layers through hydrogen or van der Waals (vdW) forces. [1] In comparison to traditional bulk MOFs, layered MOFs offer unique advantages in reaching much larger surface to volume ratios and high surface reactivity/sensitivity. [2] In particular, layered MOFs involving transition-metal cations are interesting owing to their partially filled orbitals with unique magnetic properties. [3] Liu et al. has demonstrated that a high capacity electrode based on Mn MOFs shows great potential application in supercapacitors. [4] Munn et al. investigated MIL-47 (Mn) containing both 1,4-benzenedicarboxylate (BDC) and pyridine-N-oxide (PNO) linkers exhibits anti-ferromagnetic behavior at low temperature. [5] Despite their potential, the studies to date have shown that it is hard to control the microstructure and crystallinity of Mn MOFs. One of the challenges encountered in the synthesis of Mn MOFs is the low electronegativity of Mn. Historically, the low electronegativity in titanium has hindered the fabrication of Ti-based MOFs with controllable crystallinity. The nature of ease of losing outer electrons in Ti leads to the intense electrostatic between TiÀO. The formed strong TiÀO bonds significantly impedes the ligand exchange process which is vital to control over MOF crystallinity. Although the modulation of Ti (or other Group 4 metals) MOFs synthesis via unidentate molecules (such as formic acid, pyridine, ethanol) is wellestablished, [6] there is no efficient way to gain control over the formation of Mn MOFs, let alone the precise manipulation in the reduced dimensionality (2D) landscape.Previou...

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A Redox‐Active 2D Metal–Organic Framework for Efficient Lithium Storage with Extraordinary High Capacity

Cited by 195 publications

References 28 publications

A Two‐Dimensional Metal–Organic Polymer Enabled by Robust Nickel–Nitrogen and Hydrogen Bonds for Exceptional Sodium‐Ion Storage

A Two‐Dimensional Metal–Organic Polymer Enabled by Robust Nickel–Nitrogen and Hydrogen Bonds for Exceptional Sodium‐Ion Storage

Progress and Perspective of Metal‐ and Covalent‐Organic Frameworks and their Derivatives for Lithium‐Ion Batteries

Achieving Morphological Control over Lamellar Manganese Metal‐Organic Framework through Modulated Bi‐Phase Growth

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