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An Ostwald ripening route towards Ni-rich layered cathode material with cobalt-rich surface for lithium ion battery

奥斯特瓦尔德熟化法制备具有富钴表层的锂离子电池高镍正极材料

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Abstract

An Ostwald ripening-based route is proposed to prepare Ni-rich layered cathodes with Co-rich surface for lithium-ion batteries (LIBs). Commercially available Ni0.8Co0.1 Mn0.1(OH)2 and spray pyrolysis derived porous Co3O4 are used as mixed precursors. During the lithiation reaction process under high-temperature, the porous Co3O4 microspheres scatter primary particles and spontaneously redeposit on the surface of Ni-rich spheres according to Ostwald ripening mechanism, forming the Ni-rich materials with Co-rich outer layers. When evaluated as cathode for LIBs, the resultant material shows ability to inhibit the cation disorder, relieves the phase transition from H2 to H3 and diminishes side reactions between the electrolyte and Ni-rich cathode material. As a result, the obtained material with Co-rich outer layers exhibits much more improved cycle and rate performance than the material without Co-rich outer layers. Particularly, NCM-Co-1 (molar ratio of Ni0.8Co0.1Mn0.1(OH)2/Co3O4 is 60:1) delivers a reversible capacity of 159.2 mA h g−1 with 90.5% capacity retention after 200 cycles at 1 C. This strategy provides a general and efficient way to produce gradient substances and to address the surface problems of Ni-rich cathode materials.

摘要

本文提出了一种基于奥斯特瓦尔德熟化制备具有富钴表面的高镍正极材料的方法. 采用了商业化的Ni0.8Co0.1Mn0.1(OH)2和喷雾热解制备了多孔Co3O4作为前驱体. 在高温固相反应锂化过程中, 多孔的Co3O4会分解成颗粒. 根据奥斯特瓦尔德熟化过程, 这些颗粒与锂盐反应并自发地沉积于高镍材料的表面, 形成具有富钴表层的高镍正极材料. 作为锂离子电池正极材料时, 改性后的材料中阳离子的混排得到抑制, H2到H3的相变程度降低, 并减少了电解液和高镍正极材料之间的副反应. 因此, 具有富钴表层的高镍正极材料相比于原始材料循环和倍率性能得到很大提升. NCM-Co-1 (Ni0.8Co0.1Mn0.1(OH)2/Co3O4的摩尔比为 60:1)在1 C下循环200次放电容量仍有159.2 mA h g−1, 容量保持率为90.5%. 这一策略为制备梯度正极材料以及解决高镍正极材料的表面问题提供了一种通用而有效的方法.

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Acknowledgements

This work has been carried out with the financial support of the National Basic Research Program of China (2014CB643406), the National Natural Science Foundation of China (51674296, 51574287, 51704332), the National Postdoctoral Program for Innovative Talents (BX201700290), and the Fundamental Research Funds for the Central Universities of Central South University (2017zzts127).

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Authors and Affiliations

  1. School of Metallurgy and Environment, Central South University, Changsha, 410083, China

    Yan Li  (李艳), Xinhai Li  (李新海), Zhixing Wang  (王志兴), Huajun Guo  (郭华军) & Jiexi Wang  (王接喜)

  2. Powder Metallurgy Research Institute, Central South University, Changsha, 410083, China

    Jiexi Wang  (王接喜)

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  1. Yan Li  (李艳)
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Correspondence to Jiexi Wang  (王接喜).

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Yan Li is now a Ph.D. student at School of Metallurgy and Environment, Central South University. She received her BSc degree (2012) and MSc degree (2015) in metallurgical engineering from Central South University (China). Her research interests include synthesis and modification of electrode materials for lithium ion battery, especially the Ni-rich cathode materials.

Jiexi Wang received his BSc degree (2010) in Metallurgical Engineering and PhD degree (2015) in Physical Chemistry of Metallurgy from Central South University (China). After working as a postdoctoral fellow at the Hong Kong University of Science & Technology and The University of Hong Kong, he started his independent research career as an Associate Professor at Central South University (China) in 2017. His research focuses on the green synthesis and application of nonferrous-based materials and composites for energy storage, such as high-power/high-energy lithium/sodium ion batteries, and supercapacitors. He has published about 80 SCI papers with ∼1600 citations (h-index=26).

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Li, Y., Li, X., Wang, Z. et al. An Ostwald ripening route towards Ni-rich layered cathode material with cobalt-rich surface for lithium ion battery. Sci. China Mater. 61, 719–727 (2018). https://doi.org/10.1007/s40843-017-9162-3

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