Spindle-like Ni3(HITP)2 MOFs: Synthesis and Li+ storage mechanism

Zhang, Yi; Qiu, Tianpei; Jiang, Fei; Amzil, Said; Wang, Yeji; Fu, Hao; Yang, Chaofan; Fang, Zebo; Huang, Junjie; Dai, Guoliang

doi:10.1016/j.apsusc.2021.149818

Cited by 27 publications

(8 citation statements)

References 58 publications

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“…As shown in Figure 2a, the N 1s high-resolution XPS spectrum of CoHP could be fitted into two peaks at 399.3 and 398.1 eV, which were assigned to the aniline amine (−NH−) and quinoid imine (�N−), respectively, in the ligand 32,37 and well correlated with the formation of CoHP. The XPS spectra of Co 2p were analyzed before and after Li 2 S 6 adsorption.…”

Section: ■ Results and Discussionmentioning

confidence: 91%

Electrostatic Potential-Induced Co–N₄ Active Centers in a 2D Conductive Metal–Organic Framework for High-Performance Lithium–Sulfur Batteries

Song

et al. 2022

ACS Appl. Mater. Interfaces

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The use of single-atom catalysts is a promising approach to solve the issues of polysulfide shuttle and sluggish conversion chemistry in lithium−sulfur (Li−S) batteries. However, a single-atom catalyst usually contains a low content of active centers because more metal ions lead to generation of aggregation or the formation of nonatomic catalysts. Herein, a 2D conductive metal−organic framework [Co 3 (HITP) 2 ] with abundant and periodic Co−N 4 centers was decorated on carbon fiber paper as a functional interlayer for advanced Li−S batteries. The Co 3 (HITP) 2 -decorated interlayer exhibits a chemical anchoring effect and facilitates conversion kinetics, thus effectively restraining the polysulfide shuttle effect. Density functional theory calculations demonstrate that the Co−N 4 centers in Co 3 (HITP) 2 feature more intense electron density and more negative electrostatic potential distribution than those in the carbon matrix as the singleatom catalyst, thereby promoting the electrochemical performance due to the lower reaction Gibbs free energies and decomposition energy barriers. As a result, the optimized batteries deliver a high rate capacity of over 400 mA h g −1 at 4 C current and a satisfying capacity decay rate of 0.028% per cycle over 1000 cycles at 1 C. The designed Co 3 (HITP) 2 -decorated interlayer was used to prepare one of the most advanced Li−S batteries with excellent performance (reversible capacity of 762 mA h g −1 and 79.6% capacity retention over 500 cycles) under high-temperature conditions, implying its great potential for practical applications.

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Section: ■ Results and Discussionmentioning

confidence: 91%

Electrostatic Potential-Induced Co–N₄ Active Centers in a 2D Conductive Metal–Organic Framework for High-Performance Lithium–Sulfur Batteries

Song

et al. 2022

ACS Appl. Mater. Interfaces

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Section: Conductive Mof Compositesmentioning

confidence: 99%

“…In 2021, a spindle-like conductive Ni 3 (HITP) 2 was synthesized and characterized as anodes for lithium storage (Figure 13d). [136] The abundant amino end groups in HITP ligand can form strong coordination bond with Ni 2+ , thus building a stable structure for the repeated insertion/ exportation of Li + . Besides, the aromatic ring and the d-orbit of Ni 2+ can form a large d-π electron conjugation system, which is favorable for electron transfer.…”

Section: Intrinsically Conductive Mofsmentioning

confidence: 99%

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Recent Progress of Advanced Conductive Metal–Organic Frameworks: Precise Synthesis, Electrochemical Energy Storage Applications, and Future Challenges

Zhu

Gao

2022

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inherent disadvantage of unstable output, which means electrochemical energy storage and conversion devices are essential for storing and utilizing these energies at any time. [6] Supercapacitors (SCs), lithium-ion batteries (LIBs), lithium-sulfur (Li-S) batteries, and electrochemical water splitting can efficiently convert electricity into chemical energy for storage and thus have received extensive attention. [7] The performance of the energy storage devices mainly depends on the electrode materials and the performance of energy conversion devices mainly depends on catalysts. Therefore, the development of high-performance electrode materials and electrocatalysts is crucial.Metal-organic frameworks (MOFs), also known as porous coordination polymers, are a new type of porous crystalline material. [8] Obtained by bridging metal ions or clusters and organic ligands via well-defined coordination bonds, MOFs possess unique structures with ultrahigh specific surface area, tunable composition, adjustable pore structure, and abundant exposed active sites, exhibiting significant potential for applications in gas storage and separation, catalysis, sensing, and energy storage. [9,10] The regular open pore structures of MOFs enable them to effectively contact electrolytes and alleviate volume expansion during charging and discharging when serving as electrodes. Besides, the abundant exposed active sites and the ultrahigh specific surface area of MOFs can meet the performance requirements of electrocatalysts for water splitting and electrode materials for SCs and LIBs, the plentiful polar sites and the complex pore structure of MOFs can effectively adsorb polysulfides as sulfur host. [11,12] Therefore, in recent years, great efforts have been devoted to the use MOFs as electrode materials for supercapacitors, anode materials for LIBs, sulfur hosts for Li-S batteries, and electrocatalysts for water splitting.The pristine MOFs possess numerous electrochemically active sites, which are almost fully accessible due to the regular pore structures. However, MOFs are usually composed of metal ions and redox-inactive organic ligands, lack free charge carriers, and charge transport paths, and thus are mostly electrically insulating, meaning that only the part in contact with current collectors or conductive additives can gain electrons to participate in the reaction, resulting in low utilization of Metal-organic frameworks (MOFs) with diverse composition, tunable structure, and unique physicochemical properties have emerged as promising materials in various fields. The tunable pore structure, abundant active sites, and ultrahigh specific surface area can facilitate mass transport and provide outstanding capacity, making MOFs an ideal active material for electrochemical energy storage and conversion. However, the poor electrical conductivity of pristine MOFs severely limits their applications in electrochemistry. Developing conductive MOFs has proved to be an effective solution to this problem. This review focuses on the design and syn...

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“…[3,5,6] Typically, to enhance Li + -storage in LIBs, the efforts on electrode materials mainly focused on organic materials with "Superlithiation" performance, which incorporated multiple, stable, and reversible redox groups in the conjugated skeleton (such as benzene rings and triazine rings), forming Li 6 C 6 or Li 6 C 3 N 3 . [7][8][9][10][11][12][13] For these redox organic materials, there still have some intrinsic issues needed to be overcome, including insufficient ion diffusion kinetics, which leads to not only a low capacity but also unsatisfied rate capacity and cycling performance. [14][15][16][17][18][19] In theory, the positively charged skeleton facilitates Li + fast migration in the conjugated chains, benefiting for redox PILs to realize the superlithiation performance, which is very promising to solve the problem of the slow ion diffusion kinetics in organic electrode materials.…”

Section: Introductionmentioning

confidence: 99%

Superlithiation Performance of Pyridinium Polymerized Ionic Liquids with Fast Li⁺ Diffusion Kinetics as Anode Materials for Lithium‐Ion Battery

Wang

Yang

Wang

et al. 2023

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Polymerized ionic liquids (PILs) with super ion diffusion kinetics have aroused considerable attention in rechargeable batteries, which are very promising to solve the problem of the slow ion diffusion kinetics in organic electrode materials. Theoretically, PILs incorporated redox groups are very suitable as anode materials to realize “superlithiation” performance, achieving high lithium storage capacity. In this study, redox pyridinium‐based PILs (PILs‐Py‐400) have been synthesized through trimerization reactions by pyridinium ionic liquids with cyano groups under an appropriate temperature (400 °C). The positively charged skeleton, extended conjugated system, abundant micropores, and amorphous structure for PILs‐Py‐400 can boost the utilization efficiency of redox sites. A high capacity of 1643 mAh g−1 at 0.1 A g−1 (96.7% of the theoretical capacity) has been obtained, indicating intriguing 13 Li+ redox reactions in per repeating unit of one pyridinium ring, one triazine ring, and one methylene. Moreover, PILs‐Py‐400 exhibit excellent cycling stability with a capacity of around 1100 mAh g−1 at 1.0 A g−1 after 500 cycles, and the capacity retention is 92.2%.

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Spindle-like Ni3(HITP)2 MOFs: Synthesis and Li+ storage mechanism

Cited by 27 publications

References 58 publications

Electrostatic Potential-Induced Co–N₄ Active Centers in a 2D Conductive Metal–Organic Framework for High-Performance Lithium–Sulfur Batteries

Electrostatic Potential-Induced Co–N₄ Active Centers in a 2D Conductive Metal–Organic Framework for High-Performance Lithium–Sulfur Batteries

Recent Progress of Advanced Conductive Metal–Organic Frameworks: Precise Synthesis, Electrochemical Energy Storage Applications, and Future Challenges

Superlithiation Performance of Pyridinium Polymerized Ionic Liquids with Fast Li⁺ Diffusion Kinetics as Anode Materials for Lithium‐Ion Battery

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Spindle-like Ni3(HITP)2 MOFs: Synthesis and Li+ storage mechanism

Cited by 27 publications

References 58 publications

Electrostatic Potential-Induced Co–N4 Active Centers in a 2D Conductive Metal–Organic Framework for High-Performance Lithium–Sulfur Batteries

Electrostatic Potential-Induced Co–N4 Active Centers in a 2D Conductive Metal–Organic Framework for High-Performance Lithium–Sulfur Batteries

Recent Progress of Advanced Conductive Metal–Organic Frameworks: Precise Synthesis, Electrochemical Energy Storage Applications, and Future Challenges

Superlithiation Performance of Pyridinium Polymerized Ionic Liquids with Fast Li+ Diffusion Kinetics as Anode Materials for Lithium‐Ion Battery

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Product

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Electrostatic Potential-Induced Co–N₄ Active Centers in a 2D Conductive Metal–Organic Framework for High-Performance Lithium–Sulfur Batteries

Electrostatic Potential-Induced Co–N₄ Active Centers in a 2D Conductive Metal–Organic Framework for High-Performance Lithium–Sulfur Batteries

Superlithiation Performance of Pyridinium Polymerized Ionic Liquids with Fast Li⁺ Diffusion Kinetics as Anode Materials for Lithium‐Ion Battery