Covalent Organic Framework with Highly Accessible Carbonyls and π‐Cation Effect for Advanced Potassium‐Ion Batteries

Luo, Xiaomin; Li, Wenhao; Liang, Hao‐Jie; Zhang, Hongxia; Du, Kai‐Di; Wang, Xiaotong; Liu, Xinfang; Zhang, Jingping; Wu, Xing‐Long

doi:10.1002/ange.202117661

Cited by 23 publications

(9 citation statements)

References 76 publications

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“…The initial Coulombic efficiency is 42.7% due to an irreversible discharged capacity loss in this cycle, which was probably related to the formation of a solid electrolyte interphase (SEI) for this porous HAN-Cu-MOF anode. 51 As a comparison, the HAN molecule anode delivered a lower reversible capacity of 120.8 mAh g −l at 50 mA g −1 (Figures 2a and S15). Cyclic voltammetry (CV) tests were performed to probe the behavior of electrochemical reactions.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Conductive Metal–Organic Framework with Superior Redox Activity as a Stable High-Capacity Anode for High-Temperature K-Ion Batteries

Yang,

Zeng,

Xie

et al. 2024

J. Am. Chem. Soc.

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High-temperature rechargeable batteries are essential for energy storage in elevated-temperature situations. Due to the resource abundance of potassium, hightemperature K-ion batteries are drawing increasing research interest. However, raising the working temperature would aggravate the chemical and mechanical instability of the KIB anode, resulting in very fast capacity fading, especially when high capacity is pursued. Here, we demonstrated that a porous conductive metal−organic framework (MOF), which is constructed by N-rich aromatic molecules and CuO 4 units via π−d conjugation, could provide multiple accessible redox-active sites and promised robust structure stability for efficient potassium storage at high temperatures. Even working at 60 °C, this MOF anode could deliver high initial capacity (455 mAh g −1 ), impressive rate, and extraordinary cyclability (96.7% capacity retention for 1600 cycles), which is much better than those of reported high-temperature KIB anodes. The mechanistic study revealed that C�N groups and CuO 4 units contributed abundant redox-active sites; the synergistic effect of π−d conjugated character and reticular porous architecture facilitated the K + /e − transport and ensured an insoluble electrode with small volume deformation, thus achieving stable high-capacity potassium storage.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Conductive Metal–Organic Framework with Superior Redox Activity as a Stable High-Capacity Anode for High-Temperature K-Ion Batteries

Yang,

Zeng,

Xie

et al. 2024

J. Am. Chem. Soc.

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“…The local minimum points on the van der Waals (vdW) surface are symmetrically distributed on both sides of this plane (Figure 2d), suggesting that Na + may be further adsorbed on the π-conjugated framework of HHTP-TABQ +24Na to obtain a higher reversible capacity than the theoretical value due to the π-cation effect. 14 Due to the deep degree of cross-linking, polymer electrodes are generally less conductive but have high stability in organic liquid electrolytes (Figure S10). Therefore, ester-based electrolytes (1 M NaClO 4 ethylene carbonate (EC)/dimethyl carbonate (DMC) with 5 wt % fluoroethylene carbonate (FEC) electrolyte) and carbon nanotubes (CNTs) were selected to make up this deficiency to evaluate the sodiumstorage performances of HHTP-TABQ COF.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The slope b was calculated proximate to 1.0 (0.87 for the oxidation peak and 0.95 for the reduction peak), indicating that the fast kinetics of HHTP-TABQ COF are simultaneously contributed by ionic diffusion and capacitive ion adsorption, and the capacitive behavior dominates a large proportion during the sodiation process. 14,41 The contributions of Faradaic diffusion processes (k 1 v) and capacitive behavior (k 2 v 1/2 ) at different scan rates can be discriminated according to the following equation 46,47…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…13 Moreover, the conjugated frameworks could allow π-electrons highly delocalized with ultra-stability, which is favorable for electron transfer and of great significance to promoting electrode conductivity. 14 Unlike organic small molecules, COF materials are stable in most organic solvents. The inherent insolubility effectively inhibits their severe dissolution in conventional liquid organic electrolytes for achieving great cycling stability.…”

Section: ■ Introductionmentioning

confidence: 99%

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Two-Dimensional Covalent Organic Framework with Synergistic Active Centers for Efficient Electrochemical Sodium Storage

et al. 2023

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Benefiting from the adjustable molecule structures, abundant functional units, large specific surface areas, and ordered pores, covalent organic frameworks (COFs) are highly desirable for electrochemical energy storage. Herein, a two-dimensional COF (denoted as HHTP-TABQ) with a fully π-conjugated framework and C�N and C�O dual-active sites has been synthesized and applied as the anode in organic rechargeable sodium-ion batteries (SIBs). During the sodium-storage process, it delivered remarkable rate capability, satisfactory ultra-long cycle stability (84.5% capacity retention ratio after 1000 cycles at 5000 mA g −1 ), and facile charge exchange kinetics (2.49 × 10 −7 cm 2 s −1 ), which is superior among most reported COF-based electrodes. Furthermore, the sodiation mechanism was investigated by density functional theory calculations and ex situ characterizations, which confirms that the electrochemical reaction is dominated by the synergistic reaction of C�N and C�O groups. These results suggest that COFs with stable π-conjugated structures, insoluble characteristics, and abundant active sites would have great potential for practical applications in rechargeable SIBs.

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“…Benefited from the thin coating providing more active sites exposed and the π ‐cation interaction between π ‐conjugated benzene rings and K + ions, COF‐10@CNT composite exhibits high K‐ion storage with a stable capacity of 288 mAh g –1 after 500 cycles at 0.1 A g –1 , much larger than that (57 mAh g –1 ) for COF‐10. Another, Wu and co‐workers 149 conducted the in situ condensation of anhydride and amine in the presence of single‐wall CNT (SWCNT), as a result coating a PI‐COF layer onto SWCNT. The synergistic effects between PI‐COF providing numerous active sites and SWCNT ensuring fast electron transfer, allow a specific capacity of 438 mA h g −1 and excellent cyclic stability for the resulting polyimide COF@SWCNT composites when they were used as advanced anode for PIBs.…”

Section: Composite Microstructures Of Cofsmentioning

confidence: 99%

Multi‐scale structure engineering of covalent organic framework for electrochemical charge storage

Zhang,

Li,

Yang

et al. 2023

SusMat

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Covalent organic frameworks (COFs), which are constructed by linking organic building blocks via dynamic covalent bonds, are newly emerged and burgeoning crystalline porous copolymers with features including programmable topological architecture, pre‐designable periodic skeleton, well‐defined micro‐/meso‐pore, large specific surface area, and customizable electroactive functionality. Those benefits make COFs as promising candidates for advanced electrochemical energy storage. Especially, for now, structure engineering of COFs from multi‐scale aspects has been conducted to enable optimal overall electrochemical performance in terms of structure durability, electrical conductivity, redox activity, and charge storage. In this review, we give a fundamental and insightful study on the correlations between multi‐scale structure engineering and eventual electrochemical properties of COFs, started with introducing their basic chemistries and charge storage principles. The careful discussion on the significant achievements in structure engineering of COFs from linkages, redox sites, polygon skeleton, crystal nanostructures, and composite microstructures, and further their effects on the electrochemical behavior of COFs are presented. Finally, the timely cutting‐edge perspectives and in‐depth insights into COF‐based electrode materials to rationally screen their electrochemical behaviors for addressing future challenges and implementing electrochemical energy storage applications are proposed.

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Covalent Organic Framework with Highly Accessible Carbonyls and π‐Cation Effect for Advanced Potassium‐Ion Batteries

Cited by 23 publications

References 76 publications

Conductive Metal–Organic Framework with Superior Redox Activity as a Stable High-Capacity Anode for High-Temperature K-Ion Batteries

Conductive Metal–Organic Framework with Superior Redox Activity as a Stable High-Capacity Anode for High-Temperature K-Ion Batteries

Two-Dimensional Covalent Organic Framework with Synergistic Active Centers for Efficient Electrochemical Sodium Storage

Multi‐scale structure engineering of covalent organic framework for electrochemical charge storage

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