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A Li-rich layered-spinel cathode material for high capacity and high rate lithium-ion batteries fabricated via a gas-solid reaction

通过气固反应制备高容量和高倍率性能的层状-尖晶石复合正极材料

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Abstract

Lithium-rich layered oxide (LLO) cathode materials have drawn extensive attention due to their ultrahigh specific capacity and energy density. However, their commercialization is still restricted by their low initial coulombic efficiency, slow intrinsic kinetics and structural instability. Herein, a facile surface treatment strategy via gaseous phosphine was designed to improve the rate performance and capacity stability of LLOs. During the solid-gas reaction, phosphine reacted with active oxygen at the surface of LLOs due to its reductivity, forming oxygen vacancies and spinel phase at the surface region. As a result, Li ion conductivity and structural stability were greatly enhanced. The phosphinetreated LLOs (LLO@P) showed a layered-spinel hybrid structure and delivered an outstanding rate performance of 156.7 mA h g−1 at 10 C and a high capacity retention of 74% after 300 cycles at 5 C.

摘要

富锂材料具有较高的比容量和能量密度, 因而受到了广泛关 注. 但是富锂材料仍然面临着库伦效率低、动力学性能差以及结 构稳定性差等缺点, 限制了其进一步的商业化应用. 本文中通过气 相的磷化氢对富锂材料进行热处理, 来提高其倍率性能和循环稳 定性. 在热处理过程中, 具有较高还原活性的磷化氢会与富锂材料 的表面活性氧原子进行反应, 进而在材料表面生成氧空穴和尖晶 石相结构. 改性后, 富锂材料的锂离子电导率和结构稳定性显著提 升, 当以1 0 C的大电流进行充放电时, 放电比容量可达 156.7 mA h g−1, 在5 C下循环300圈后容量保持率仍然可达74%.

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Acknowledgements

The authors gratefully acknowledge the financial support from the Ministry of Science and Technology of China (MoST, 2016YFA0200200), the National Natural Science Foundation of China (NSFC, 21421001 and 51633002), Tianjin city (16ZXCLGX00100) and 111 Project (B12015).

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. School of Materials Science and Engineering, Nankai University, Tianjin, 300071, China

    Lingqun Xu  (徐灵群)

  2. The Centre of Nanoscale Science and Technology and Key Laboratory of Functional Polymer Materials, Nankai University, Tianjin, 300071, China

    Zhenhe Sun  (孙振贺), Yu Zhu  (朱玉), Yu Han  (韩宇), Manman Wu  (吴蔓蔓), Yanfeng Ma  (马延风), Hongtao Zhang  (张洪涛) & Yongsheng Chen  (陈永胜)

  3. The National Institute for Advanced Materials, Nankai University, Tianjin, 300071, China

    Lingqun Xu  (徐灵群), Yanfeng Ma  (马延风), Yi Huang  (黄毅), Hongtao Zhang  (张洪涛) & Yongsheng Chen  (陈永胜)

Authors
  1. Lingqun Xu  (徐灵群)
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  2. Zhenhe Sun  (孙振贺)
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  3. Yu Zhu  (朱玉)
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  4. Yu Han  (韩宇)
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  6. Yanfeng Ma  (马延风)
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  8. Hongtao Zhang  (张洪涛)
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  9. Yongsheng Chen  (陈永胜)
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Contributions

Chen Y conceived and designed the research; Xu L fabricated the cathode materials and assembled the cells; Sun Z conducted partial characterization and analyses; Zhu Y, Han Y, Wu M, Ma Y and Huang Y were involved in some experiments; Xu L and Zhang H wrote the paper, with support from Chen Y; Chen Y and Zhang H coordinated the study. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Hongtao Zhang  (张洪涛) or Yongsheng Chen  (陈永胜).

Additional information

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Experimental details and supporting data are available in the online version of the paper.

Lingqun Xu received her BS degree in polymer material and engineering from Yanshan University Now as a postgraduate in Nankai University, her research mainly focuses on improving the electrochemical performances of lithium-rich cathode materials and lithium sulfur batteries

Zhenhe Sun received his BE and BS degrees from the Molecular Science and Engineering department of Nankai University in 2015. He is currently studying for a doctoral degree in Prof. Yongsheng Chen’s Group. His research interests include the syntheses and modifications of lithium-rich cathode materials and supercapacitors based on carbon materials.

Hongtao Zhang received his PhD degree from the Institute of Chemistry, Chinese Academy of Sciences (ICCAS) in 2012. He joined Prof. Yongsheng Chen’s group at Nankai University in 2014. His current research interests mainly focus on the syntheses and characterizations of organic and polymer functional materials and their applications in energy conversion and storage devices.

Yongsheng Chen graduated from the University of Victoria with a PhD degree in chemistry in 1997 and then joined the University of Kentucky and the University of California at Los Angeles for postdoctoral studies from 1997 to 1999. From 2003, he has been a Chair Professor at Nankai University. His main research interests include: i) carbon-based nanomaterials, including carbon nanotubes and graphene; ii) organic and polymeric functional materials, and iii) energy devices including organic photovoltaics and supercapacitors.

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40843_2020_1433_MOESM1_ESM.pdf

A Li-rich layered-spinel cathode material for high capacity and high rate lithium-ion batteries fabricated via a gas-solid reaction

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Xu, L., Sun, Z., Zhu, Y. et al. A Li-rich layered-spinel cathode material for high capacity and high rate lithium-ion batteries fabricated via a gas-solid reaction. Sci. China Mater. 63, 2435–2442 (2020). https://doi.org/10.1007/s40843-020-1433-4

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  • DOI: https://doi.org/10.1007/s40843-020-1433-4

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