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Supramolecular self-assembly synthesis of hemoglobin-like amorphous CoP@N, P-doped carbon composites enable ultralong stable cycling under high-current density for lithium-ion battery anodes

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Abstract

Cobalt phosphide (CoP) has been emerging as alternative lithium-ion batteries (LIBs) anode in view of the outstanding thermodynamic stability and high theoretical capacity. However, the lithium storage behaviors were impeded by poor cycling and rate performance induced by huge volumetric changes of CoP anodes during Li+ intercalation/deintercalation and the poor reaction kinetics caused by low electronic conductivity. Herein, the uniquely designed hemoglobin-like composites consisting of CoP nanoparticles coated by N, P-doped carbon shell (CoP@PNC) were prepared via a supramolecular self-assembly method, followed by the facile heat treatment process, which presented the amorphous phase. Based on the synergistic effects of rational nano/microstructure, double heterogeneous elements doped carbon substrate and amorphous phase, the transport paths of Li+ and e− were shortened, the electronic conductivity was enhanced, the volumetric changes were effectively alleviated, resulting in outstanding electrochemical performance when applied as anode electrodes. The CoP@PNC electrodes deliver a capacity of 806.8 mAh g−1 after 100 cycles at 0.1 A g−1 and 523.9 mAh g−1 after 3000 cycles at 2.0 A g−1. Furthermore, pseudo-capacitance behavior dominates the storage mechanism of CoP@PNC electrodes based on the quantitative kinetic analysis result that a high ratio of 66% in total capacity at 0.5 mV−1. This work illuminates the route to effectively relieve the huge volumetric changes to improve the electrochemical performance of transition metal phosphide and promote their practical application steps as electrodes for high energy density batteries.

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Funding

This work was supported by the National Natural Science Foundation of China (52207249), the research program of the top talent project of Yantai University (1115/2220001), the Yantai basic research project (2022JCYJ04), and the science fund of the Shandong Laboratory of Advanced Materials and Green Manufacturing (AMGM2021F11).

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Authors and Affiliations

  1. School of Environmental and Material Engineering, Yantai University, No. 30 Qingquan Road, Shandong, Yantai, 264005, China

    Qin Mu, Ruilin Liu, Hideo Kimura, **cheng Li, Huiyu Jiang, **aoyu Zhang, Zhipeng Yu, Xueqin Sun, Wei Du & Chuanxin Hou

  2. Shandong Laboratory of Yantai Advanced Materials and Green Manufacturing, Shandong, Yantai, 264005, China

    **aoyu Zhang

  3. College of Materials Science and Engineering, Taiyuan University of Science and Technology, Shanxi, Taiyuan, 030024, China

    **aoyu Zhang

  4. Department of Electrical Engineering, Faculty of Engineering, Najran University, Najran, 11001, Saudi Arabia

    Hassan Algadi

  5. Mechanical and Construction Engineering, Faculty of Engineering and Environment, Northumbria University, Newcastle Upon Tyne, NE1 8ST, UK

    Zhanhu Guo

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  1. Qin Mu
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  2. Ruilin Liu
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  3. Hideo Kimura
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  11. Wei Du
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Contributions

Per the journal requirement of more than ten contributors, the required contribution can be briefly stated as Qin Mu, Huiyu Jiang, Hideo Kimura, Ruilin Liu, and **cheng Li make the samples and property characterizations; **aoyu Zhang, Zhipeng Yu, Xueqin Sun, and Chuanxin Hou inputted the electrochemical analysis and characterization; Chuanxin Hou, Hassan Algadi, Zhanhu Guo, and Wei Du* made the detailed experimental design and organize the paper. All authors have read the paper, modified the final version, and agreed on the submission.

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Correspondence to Zhipeng Yu, Zhanhu Guo, Wei Du or Chuanxin Hou.

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Mu, Q., Liu, R., Kimura, H. et al. Supramolecular self-assembly synthesis of hemoglobin-like amorphous CoP@N, P-doped carbon composites enable ultralong stable cycling under high-current density for lithium-ion battery anodes. Adv Compos Hybrid Mater 6, 23 (2023). https://doi.org/10.1007/s42114-022-00607-y

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