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Nano Research 2024, 17(6): 5122-5130 https://doi.org/10.1007/s12274-024-6424-9
Research Article | Issue | Published: 13 January 2024

Ni/Co bimetallic organic frameworks nanospheres for high-performance electrochemical energy storage

Show Author's Information Jianru Guan1,  Minlu Liu1,  Limin Zhu1( ),  Jiamei Wang1,  Qing Han1,  Xiaoxia Yang2,  Weibo Hua2( ),  Lingling Xie3( ),  Xiaoyu Cao1( )
School of Chemistry and Chemical Engineering, Key Laboratory of High Specific Energy Materials for Electrochemical Power Sources of Zhengzhou City, Henan University of Technology, Zhengzhou 450001, China
School of Chemical Engineering and Technology, Xi’an Jiaotong University, Xi’an 710049, China
School of Environmental Engineering, Henan University of Technology, Zhengzhou 450001, China
Keywords:
lithium-ion batteries, electrochemical energy storage, metal organic frame, dual ligand, hard-soft-acid-base
Topics:
Lithium batteries
Cite this article:
Guan J, Liu M, Zhu L, et al. Ni/Co bimetallic organic frameworks nanospheres for high-performance electrochemical energy storage. Nano Research, 2024, 17(6): 5122-5130. https://doi.org/10.1007/s12274-024-6424-9
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Abstract Full text Electronic supplementary material About this article

In addition to their many well-known advantages (e.g., ultra-high porosity, good pore size distribution, easy functionalization, and structural tolerability), metal-organic frameworks (MOFs) are a new class of advanced functional materials. However, their backbones are highly susceptible to deformation after exposure to acidic or alkaline conditions. As a result of lithium-ion batteries embedding or detaching directly from MOFs, they irreversibly collapse. As a result, they fail to maintain their electrochemical performance. These factors have hindered the development of MOFs as direct electrode materials, making the design of MOF materials with controlled morphology and stable dimensions a new challenge. In this study, we adopted a versatile and effective method to synthesize a novel MOF material (NiCo-BP (BP = BTC/phen and BTC = 1,3,5-benzenetricarboxylic acid)) using the rigid ligands 1,10-phenanthroline and homobenzotrizoic acid, and the emergence of the Ni–O/N and Co–O/N coordination layers was observed by extended X-ray absorption fine structure (EXAFS) tests, indicating that Ni and Co were coordinated with heterocyclic N-given atoms to form a stable p–π conjugated structure. Meanwhile, the metal-ion is attached to the carboxylic acid ligand on the other side, making the metal-organic skeleton complete and robust. The nanosphere structure of NiCo-BP (~ 400 nm) allows for full exposure and utilisation of the active sites, especially the Ni, Co, and phenanthroline units, and exhibit impressively high specific capacity and cycling stability. At a high current density of 1.0 A·g−1, a high discharge specific capacity of 631.6 mAh·g−1 was obtained after 1000 cycles. The co-participation of two organic ligands in the coordination is in accordance with the theory of soft and hard acids and bases, which contributes to the ability of the material to maintain a high capacity in cycling as well as its cyclic stability.


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Abstract
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Electronic supplementary material
About this article

Ni/Co bimetallic organic frameworks nanospheres for high-performance electrochemical energy storage

Show Author's information Jianru Guan1, Minlu Liu1, Limin Zhu1( ), Jiamei Wang1, Qing Han1, Xiaoxia Yang2, Weibo Hua2( ), Lingling Xie3( ), Xiaoyu Cao1( )
School of Chemistry and Chemical Engineering, Key Laboratory of High Specific Energy Materials for Electrochemical Power Sources of Zhengzhou City, Henan University of Technology, Zhengzhou 450001, China
School of Chemical Engineering and Technology, Xi’an Jiaotong University, Xi’an 710049, China
School of Environmental Engineering, Henan University of Technology, Zhengzhou 450001, China

Abstract

In addition to their many well-known advantages (e.g., ultra-high porosity, good pore size distribution, easy functionalization, and structural tolerability), metal-organic frameworks (MOFs) are a new class of advanced functional materials. However, their backbones are highly susceptible to deformation after exposure to acidic or alkaline conditions. As a result of lithium-ion batteries embedding or detaching directly from MOFs, they irreversibly collapse. As a result, they fail to maintain their electrochemical performance. These factors have hindered the development of MOFs as direct electrode materials, making the design of MOF materials with controlled morphology and stable dimensions a new challenge. In this study, we adopted a versatile and effective method to synthesize a novel MOF material (NiCo-BP (BP = BTC/phen and BTC = 1,3,5-benzenetricarboxylic acid)) using the rigid ligands 1,10-phenanthroline and homobenzotrizoic acid, and the emergence of the Ni–O/N and Co–O/N coordination layers was observed by extended X-ray absorption fine structure (EXAFS) tests, indicating that Ni and Co were coordinated with heterocyclic N-given atoms to form a stable p–π conjugated structure. Meanwhile, the metal-ion is attached to the carboxylic acid ligand on the other side, making the metal-organic skeleton complete and robust. The nanosphere structure of NiCo-BP (~ 400 nm) allows for full exposure and utilisation of the active sites, especially the Ni, Co, and phenanthroline units, and exhibit impressively high specific capacity and cycling stability. At a high current density of 1.0 A·g−1, a high discharge specific capacity of 631.6 mAh·g−1 was obtained after 1000 cycles. The co-participation of two organic ligands in the coordination is in accordance with the theory of soft and hard acids and bases, which contributes to the ability of the material to maintain a high capacity in cycling as well as its cyclic stability.

Keywords: lithium-ion batteries, electrochemical energy storage, metal organic frame, dual ligand, hard-soft-acid-base

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Publication history
Copyright
Acknowledgements

Publication history

Received: 07 October 2023
Revised: 11 December 2023
Accepted: 17 December 2023
Published: 13 January 2024
Issue date: June 2024

Copyright

© Tsinghua University Press 2024

Acknowledgements

Acknowledgements

This work was supported by National Natural Science Foundation of China (Nos. 52071132, 52261135632, U21A20284, and 52371237), Program for Innovative Team (in Science and Technology) in University of Henan Province, China (No. 24IRTSTHN006), Natural Science Foundation of Henan, China (Nos. 232300421080 and 222300420138), Science and Technology Project of Henan Province, China (Nos. 232102241038 and 232102241004), Key Scientific Research Programs in Universities of Henan Province, China–Special Projects for Basic Research (No. 23ZX008), and Innovative Funds Plan of Henan University of Technology, China (No. 2020ZKCJ04).

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