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All-dry solid-phase synthesis of single-crystalline Ni-rich ternary cathodes for lithium-ion batteries

全干法合成锂离子电池用高镍三元单晶颗粒及性能

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Abstract

Single-crystalline ternary cathodes prepared through all-dry solid-phase synthesis (ADSPS) are perceived as prominent candidates for lithium-ion batteries (LIBs) because they are inexpensive and effluent-free. However, the aggravated lithium/oxygen (Li/O) loss and sluggish lithiation process during sintering result in an unstable layered structure and a large amount of surface residual alkali. Herein, a lithium borate (LBO)-coated and strontium/titanium (Sr/Ti) co-doped single-crystalline nickel (Ni)-rich ternary cathode with a highly ordered layered structure is prepared via ADSPS for the first time. The synergistic effect of Sr/Ti ions considerably promotes grain growth with decreased lithiation temperature, which alleviates the Li/Ni disorder and stabilizes the lattice O. After coating with a layer of LBO, the surface residual alkali has been considerably depleted with favorable Li-ion transfer at the interface. Consequently, the as-obtained cathode delivers a high reversible capacity of 191.1 mA h g−1 at 0.1 C in coin-type half cells and superior retention of 90.1% after 500 cycles at 1 C in pouch-type full cells. The unique insight and strategy in this research will promote the application of ADSPS in single-crystalline Ni-rich ternary cathodes for LIBs.

摘要

单晶型高镍三元层状氧化物凭借高能量密度、 长循环寿命和优异的安全性成为新一代锂离子电池理想的正极材料. 目前, 单晶型高镍三元正极通过“共沉淀+高温锂化”两步制备, 不仅工艺繁琐、 原材料选择单一, 制备过程还会产生大量废水/气. 本文提出了一种新的全干法固相合成策略, 实现了单晶型高镍三元正极低成本、 无废水绿色制备. 在煅烧过程引入锶/钛离子作为烧结助剂, 降低烧结温度来缓解锂/氧流失, 从而降低锂镍混排并稳定晶格氧. 此外, 针对固相合成过程锂化动力学缓慢导致表面残碱较高的问题, 引入硼化合物与残碱反应, 不仅有效提升了界面稳定性, 而且形成的离子导体还能够加速锂离子在界面处的迁移. 因此, 制备的单晶型高镍三元正极在0.1 C电流密度下比容量可达到191.1 mA h g−1, 以1 C电流密度在软包全电池中循环500次后仍具有90.1%的容量保持率.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (U22A20429 and 22308103), China Postdoctoral Science Foundation (2023M731083), and the Fundamental Research Funds for the Central Universities.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, 200237, China

    Li Qin  (秦理), Xin Jiang  (姜昕), Ling Chen  (陈灵), Qilin Cheng  (程起林) & Hao Jiang  (江浩)

  2. Key Laboratory for Ultrafine Materials of Ministry of Education, School of Chemical Engineering, East China University of Science and Technology, Shanghai, 200237, China

    Haifeng Yu  (余海峰) & Hao Jiang  (江浩)

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  1. Li Qin  (秦理)
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  2. Haifeng Yu  (余海峰)
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  3. Xin Jiang  (姜昕)
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  4. Ling Chen  (陈灵)
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  5. Qilin Cheng  (程起林)
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  6. Hao Jiang  (江浩)
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Contributions

Author contributions Qin L, Yu H, and Jiang H conceived of the idea; Qin L and Yu H performed the experiment and data analysis; Qin L, Yu H, Jiang X, and Jiang H helped discuss partial experiment data; Qin L, Yu H and Jiang H wrote the paper; Cheng Q and Chen L modified the paper. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Qilin Cheng  (程起林) or Hao Jiang  (江浩).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Supporting data are available in the online version of the paper.

Li Qin is currently a PhD candidate in materials and science engineering under the supervision of Prof. Qilin Cheng and Prof. Hao Jiang at the East China University of Science and Technology (ECUST). His research centers on all-dry synthesis and improvement mechanism of single-crystalline Ni-rich cathodes for Li-ion batteries.

Haifeng Yu received his PhD degree in materials and science engineering from the ECUST in 2022. Now, he is a postdoctor at the School of Chemical Engineering, ECUST. His research focuses on the preparation and application of cathode materials for lithium/sodium-ion batteries.

Qilin Cheng received his PhD degree in materials science and engineering from the ECUST in 2006. He served as a visiting scientist at the Faculty of Technology, Tomas Bata University (Czech Republic) between 2004 and 2008. At present, he is a professor of materials science at the ECUST. His main research area covers the preparation and application of energy storage devices and related materials.

Hao Jiang received his PhD degree in materials and science engineering from the ECUST in 2009. He then joined Temasek Laboratories, Nanyang Technological University in Singapore, as a research scientist from 2009 to 2011. Now, he is a professor of the Key Laboratory for Ultrafine Materials of the Ministry of Education at the ECUST. His research focuses on the development and applications of advanced functional materials for electrochemical energy storage and conversion.

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Qin, L., Yu, H., Jiang, X. et al. All-dry solid-phase synthesis of single-crystalline Ni-rich ternary cathodes for lithium-ion batteries. Sci. China Mater. 67, 650–657 (2024). https://doi.org/10.1007/s40843-023-2715-8

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