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Nano Research 2023, 16(4): 4908-4916 https://doi.org/10.1007/s12274-022-4485-1
Research Article | Issue | Published: 27 June 2022

In-plane grain boundary induced defect state in hierarchical NiCo-LDH and effect on battery-type charge storage

Show Author's Information Jinjin Ban1,§,  Xiaohan Wen1,2,§,  Honghong Lei3,  Guoqin Cao1,2,  Xinhong Liu1,  Chunyao Niu4,  Guosheng Shao1,2( ),  Junhua Hu1,2( )
School of Materials Science and Engineering, Industrial Technology Research Institute of Resource and Materials of Henan Province, Zhengzhou University, Zhengzhou 450001, China
State Center for International Cooperation on Designer Low-carbon & Environmental Materials (CDLCEM), Zhengzhou University, 100 Kexue Avenue, Zhengzhou 450001, China
Henan Provincial Key Laboratory for Metal Fuel Battery, Foguang Power Generation Equipment Co. Ltd, 50 Holly Street, Zhengzhou 450000, China
International Laboratory for Quantum Functional Materials of Henan, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450001, China
Jinjin Ban and Xiaohan Wen contributed equally to this work.
Keywords:
grain boundary, hierarchical structure, sacrificial template, oxygen vacancy (Vo)
Topics:
Capacitance
Cite this article:
Ban J, Wen X, Lei H, et al. In-plane grain boundary induced defect state in hierarchical NiCo-LDH and effect on battery-type charge storage. Nano Research, 2023, 16(4): 4908-4916. https://doi.org/10.1007/s12274-022-4485-1
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Abstract Full text Electronic supplementary material About this article

Domain boundaries are regarded as the effective active sites for electrochemical energy storage materials due to defects enrichment therein. However, layered double hydroxides (LDHs) tend to grow into single crystalline nano sheets due to their unique two-dimentional (2D) lattice structure. Previously, much efforts were made on the designing hierarchical structure to provide more exposed electroactive sites as well as accelerate the mass transfer. Herein, we demonstrate a strategy to introduce low angle grain boundary (LAGB) in the flakes of Ni/Co layered double hydroxides (NiCo-LDHs). These defect-rich nano flakes were self-assembled into hydrangea-like spheres that further constructed hollow cage structure. Both the formation of hierarchical structure and grain boundaries are interpreted with the synergistic effect of Ni2+/Co2+ ratio in an “etching-growth” process. The domain boundary defect also results in the preferential formation of oxygen vacancy (Vo). Additionally, density functional theory (DFT) calculation reveals that Co substitution is a critical factor for the formation of adjacent lattice defects, which contributes to the formation of domains boundary. The fabricated battery-type Faradaic NiCo-LDH-2 electrode material exhibits significantly enhanced specific capacitance of 899 C·g−1 at a current density of 1 A·g−1. NiCo-LDH-2//AC asymmetric capacitor shows a maximum energy density of 101.1 Wh·kg−1 at the power density of 1.5 kW·kg−1.


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Electronic supplementary material
About this article

In-plane grain boundary induced defect state in hierarchical NiCo-LDH and effect on battery-type charge storage

Show Author's information Jinjin Ban1,§, Xiaohan Wen1,2,§, Honghong Lei3, Guoqin Cao1,2, Xinhong Liu1, Chunyao Niu4, Guosheng Shao1,2( ), Junhua Hu1,2( )
School of Materials Science and Engineering, Industrial Technology Research Institute of Resource and Materials of Henan Province, Zhengzhou University, Zhengzhou 450001, China
State Center for International Cooperation on Designer Low-carbon & Environmental Materials (CDLCEM), Zhengzhou University, 100 Kexue Avenue, Zhengzhou 450001, China
Henan Provincial Key Laboratory for Metal Fuel Battery, Foguang Power Generation Equipment Co. Ltd, 50 Holly Street, Zhengzhou 450000, China
International Laboratory for Quantum Functional Materials of Henan, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450001, China
Jinjin Ban and Xiaohan Wen contributed equally to this work.

Abstract

Domain boundaries are regarded as the effective active sites for electrochemical energy storage materials due to defects enrichment therein. However, layered double hydroxides (LDHs) tend to grow into single crystalline nano sheets due to their unique two-dimentional (2D) lattice structure. Previously, much efforts were made on the designing hierarchical structure to provide more exposed electroactive sites as well as accelerate the mass transfer. Herein, we demonstrate a strategy to introduce low angle grain boundary (LAGB) in the flakes of Ni/Co layered double hydroxides (NiCo-LDHs). These defect-rich nano flakes were self-assembled into hydrangea-like spheres that further constructed hollow cage structure. Both the formation of hierarchical structure and grain boundaries are interpreted with the synergistic effect of Ni2+/Co2+ ratio in an “etching-growth” process. The domain boundary defect also results in the preferential formation of oxygen vacancy (Vo). Additionally, density functional theory (DFT) calculation reveals that Co substitution is a critical factor for the formation of adjacent lattice defects, which contributes to the formation of domains boundary. The fabricated battery-type Faradaic NiCo-LDH-2 electrode material exhibits significantly enhanced specific capacitance of 899 C·g−1 at a current density of 1 A·g−1. NiCo-LDH-2//AC asymmetric capacitor shows a maximum energy density of 101.1 Wh·kg−1 at the power density of 1.5 kW·kg−1.

Keywords: grain boundary, hierarchical structure, sacrificial template, oxygen vacancy (Vo)

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Publication history
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Acknowledgements

Publication history

Received: 25 January 2022
Revised: 20 March 2022
Accepted: 01 May 2022
Published: 27 June 2022
Issue date: April 2023

Copyright

© Tsinghua University Press 2022

Acknowledgements

We acknowledge financial support from the National Natural Science Foundation of China (Nos. 52171082 and 51001091) and the Program for Innovative Research Team (in Science and Technology) in University of Henan Province (No. 21IRTSTHN003). This work was also partially supported by the provincial scientific research program of Henan (No. 182102310815) and Nuclear Material Technology Innovation Fund for National Defense Technology Industry (No. ICNM-2021-YZ-02).

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