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SCIENCE CHINA Materials, Volume 61, Issue 5: 719-727(2018) https://doi.org/10.1007/s40843-017-9162-3

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

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  • ReceivedOct 10, 2017
  • AcceptedNov 17, 2017
  • PublishedDec 18, 2017

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 Ni0.8Co0.1Mn0.1(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.


Funded by

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)


Acknowledgment

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 (2017zzts125).


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Li Y, Li X and Wang J designed and engineered the samples; Li Y performed the experiments; Li Y, Wang Z, Guo H and Wang J performed the data analysis; Li Y and Wang J wrote the paper; All authors contributed to theoretical analysis and general discussion.


Author information

Yan Li is now a PhD student at the 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 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 ~1,600 citations (h-index=26).


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  • Figure 1

    Schematic diagram for the preparation of Ni-rich layered cathodes with Co-rich surface.

  • Figure 2

    XRD patterns and of NCM, NCM-Co-1 and NCM-Co-2.

  • Figure 3

    SEM images of the samples: (a) Co3O4; (b) Ni0.8Co0.1Mn0.1(OH)2; (c, d) NCM; (e, f) NCM-Co-1; (g, h) NCM-Co-2.

  • Figure 4

    EDS linear scanning analyses of particle cross sections of the samples: (a, b) NCM; (c, d) NCM-Co-1; (e, f) NCM-Co-2.

  • Figure 5

    Electrochemical performance of NCM, NCM-Co-1 and NCM-Co-2: (a) CV curves at the scan rate of 0.1 mV s−1; (b) first cycle charge/discharge profiles at 0.1 C (c) cycling performance at 1 C between 2.8 and 4.3 V and (d) rate capability in the rate range of 0.1–5 C.

  • Figure 6

    Cycling performance of NCM, NCM-Co-1 and NCM-Co-2 at 1 C after exposing to ambient air for 2 months.

  • Table 1   Lattice parameters of NCM, NCM-Co-1 and NCM-Co-2

    Sample

    a (Å)

    c (Å)

    V3)

    c/a

    I(003)/I(104)

    NCM

    2.8703

    14.1451

    100.93

    4.9281

    1.68

    NCM-Co-1

    2.8657

    14.1438

    100.78

    4.9355

    1.72

    NCM-Co-2

    2.8634

    14.1406

    100.46

    4.9384

    1.81

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