Nanostructured high-energy cathode materials for advanced lithium batteries

Nature Materials volume 11, pages942–947(2012)Cite this article

Subjects

Abstract

Nickel-rich layered lithium transition-metal oxides, LiNi1−xMxO2 (M = transition metal), have been under intense investigation as high-energy cathode materials for rechargeable lithium batteries because of their high specific capacity and relatively low cost1,2,3. However, the commercial deployment of nickel-rich oxides has been severely hindered by their intrinsic poor thermal stability at the fully charged state and insufficient cycle life, especially at elevated temperatures1,2,3,4,5,6. Here, we report a nickel-rich lithium transition-metal oxide with a very high capacity (215 mA h g−1), where the nickel concentration decreases linearly whereas the manganese concentration increases linearly from the centre to the outer layer of each particle. Using this nano-functional full-gradient approach, we are able to harness the high energy density of the nickel-rich core and the high thermal stability and long life of the manganese-rich outer layers. Moreover, the micrometre-size secondary particles of this cathode material are composed of aligned needle-like nanosize primary particles, resulting in a high rate capability. The experimental results suggest that this nano-functional full-gradient cathode material is promising for applications that require high energy, long calendar life and excellent abuse tolerance such as electric vehicles.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

Rent or Buy

All prices are NET prices.

Figure 1: Schematic diagram of the FCG lithium transition-metal oxide particle with the nickel concentration decreasing from the centre towards the outer layer and the concentration of manganese increasing accordingly.
Figure 2: SEM and EPMA results.
Figure 3: Hard X-ray nanotomography and transmission electron microscopy images.
Figure 4: Charge–discharge characteristics of IC, OC and FCG materials.
Figure 5: Contour plots of in situ HEXRD profile.

References

  1. 1

    Dunn, B., Kamath, H. & Tarascon, J. M. Electrical energy storage for the grid: A battery of choices. Science 334, 928–935 (2011).

    CAS  Article  Google Scholar 

  2. 2

    Liu, C., Li, F., Ma, L. P. & Cheng, H. M. Advanced materials for energy storage. Adv. Mater. 22, E28–E62 (2010).

    CAS  Article  Google Scholar 

  3. 3

    Scrosati, B. & Garche, J. Lithium batteries: Status, prospects and future. J. Power Sources 195, 2419–2430 (2010).

    CAS  Article  Google Scholar 

  4. 4

    Goodenough, J. B. & Kim, Y. Challenges for rechargeable Li batteries. Chem. Mater. 22, 587–603 (2010).

    CAS  Article  Google Scholar 

  5. 5

    Etacheri, V., Marom, R., Elazari, R., Salitra, G. & Aurbach, D. Challenges in the development of advanced Li-ion batteries: A review. Energ. Environ. Sci. 4, 3243–3262 (2011).

    CAS  Article  Google Scholar 

  6. 6

    Bandhauer, T. M., Garimella, S. & Fuller, T. F. A critical review of thermal issues in lithium–ion batteries. J. Electrochem. Soc. 158, R1–R25 (2011).

    CAS  Article  Google Scholar 

  7. 7

    MacNeil, D. D., Lu, Z. & Dahn, J. R. Structure and electrochemistry of Li[NixCo1−2xMnx]O2 (0< = x< = 1/2). J. Electrochem. Soc. 149, A1332–A1336 (2002).

    CAS  Article  Google Scholar 

  8. 8

    Hwang, B. J., Tsai, Y. W., Carlier, D. & Ceder, G. A combined computational/experimental study on Li[Ni1/3Co1/3Mn1/3]O2 . Chem. Mater. 15, 3676–3682 (2003).

    CAS  Article  Google Scholar 

  9. 9

    Kim, M. G., Shin, H. J., Kim, J. H., Park, S. H. & Sun, Y. K. XAS investigation of inhomogeneous metal-oxygen bond covalency in bulk and surface for charge compensation in Li-ion battery cathode Li[Ni1/3Co1/3Mn1/3]O2 material. J. Electrochem. Soc. 152, A1320–A1328 (2005).

    CAS  Article  Google Scholar 

  10. 10

    Chen, Z. H., Lee, D. J., Sun, Y-K. & Amine, K. Advanced cathode materials for lithium–ion batteries. Mater. Res. Soc. Bull. 36, 498–505 (2011).

    Article  Google Scholar 

  11. 11

    Sun, Y-K. et al. Synthesis and characterization of Li[(Ni0.8Co0.1Mn0.1)0.8(Ni0.5Mn0.5)0.2]O2 with the microscale core-shell structure as the positive electrode material for lithium batteries. J. Am. Chem. Soc. 127, 13411–13418 (2005).

    CAS  Article  Google Scholar 

  12. 12

    Sun, Y-K., Myung, S-T., Park, B-C. & Amine, K. Synthesis of spherical nano- to microscale core-shell particles Li[(Ni0.8Co0.1Mn0.1)1−x(Ni0.5Mn0.5)x]O2 and their applications to lithium batteries. Chem. Mater. 18, 5199–5163 (2006).

    Google Scholar 

  13. 13

    Sun, Y-K. et al. Novel core-shell-structured Li[(Ni0.8Co0.2)0.8(Ni0.5Mn0.5)0.2]O2 via coprecipitation as positive electrode material for lithium secondary batteries. J. Phys. Chem. B 110, 6810–6815 (2006).

    CAS  Article  Google Scholar 

  14. 14

    Sun, Y-K. et al. High-energy cathode material for long-life and safe lithium batteries. Nature Mater. 8, 320–324 (2009).

    CAS  Article  Google Scholar 

  15. 15

    Sun, Y-K. et al. A novel cathode material with a concentration-gradient for high-energy and safe lithium–ion batteries. Adv. Funct. Mater. 20, 485–491 (2010).

    Article  Google Scholar 

  16. 16

    Sun, Y-K. et al. A novel concentration-gradient Li[Ni0.83Co0.07Mn0.10]O2 cathode material for high-energy lithium–ion batteries. J. Mater. Chem. 21, 10108–10112 (2011).

    CAS  Article  Google Scholar 

  17. 17

    Berhan, L. & Sastry, A. M. Modeling percolation in high-aspect-ratio fiber systems. II. The effect of waviness on the percolation onset. Phys. Rev. E 75, 041121–041127 (2007).

    CAS  Article  Google Scholar 

  18. 18

    Shaju, K. M., Rao, G. V. S. & Chowdari, B. V. R. Li ion kinetic studies on spinel cathodes, Li(M1/6Mn11/6)O4 (M = Mn, Co, CoAl) by GITT and EIS. J. Mater. Chem. 13, 106–113 (2003).

    CAS  Article  Google Scholar 

  19. 19

    Chen, Z. H. et al. Solid state synthesis of LiFePO4 studied by in situ high energy X-ray diffraction. J. Mater. Chem. 21, 5604–5609 (2011).

    CAS  Article  Google Scholar 

  20. 20

    Chen, Z. H. et al. Multi-scale study of thermal stability of lithiated graphite. Energ. Environ. Sci. 4, 4023–4030 (2011).

    CAS  Article  Google Scholar 

  21. 21

    Ahn, D. et al. Suppression of structural degradation of LiNi0.9Co0.1O2 cathode at 90 °C by AlPO4-nanoparticle coating. Current Appl. Phys. 7, 172–175 (2007).

    Article  Google Scholar 

  22. 22

    Lee, M-H., Kang, Y-J., Myung, S-T. & Sun, Y-K. Synthetic optimization of Li[Ni1/3Co1/3Mn1/3]O2 via co-precipitation. Electrochim. Acta 50, 939–848 (2004).

    CAS  Article  Google Scholar 

  23. 23

    Hammersley, A. P., Svensson, S. O., Hanfland, M., Fitch, A. N. & Hausermann, D. Two-dimensional detector software: From real detector to idealised image or two-theta scan. High Pressure Res. 14, 235–248 (1996).

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the Human Resources Development of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korea government Ministry of Knowledge Economy (No. 20114010203150) and the National Research Foundation of KOREA (NRF) grant funded by the Korea government (MEST; No. 2009-0092780). Research at Argonne National Laboratory was funded by the US Department of Energy, EERE Vehicle Technologies Program. Argonne National Laboratory is operated for the US Department of Energy by UChicago Argonne, LLC, under contract DE-AC02-06CH11357. The authors also acknowledge the use of the Advanced Photon Source of Argonne National Laboratory supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences.

Author information

Author notes

  1. Yang-Kook Sun and Zonghai Chen: These authors contributed equally to this work

  2. yksun@hanyang.ac.kr

Affiliations

  1. Department of WCU Energy Engineering, Hanyang University, Seoul 133-791, South Korea

    Yang-Kook Sun, Hyung-Joo Noh, Dong-Ju Lee & Hun-Gi Jung

  2. Department of Chemical Engineering, Hanyang University, Seoul 133-791, South Korea

    Yang-Kook Sun

  3. Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Lemont, Illinois 60439, USA

    Zonghai Chen & Khalil Amine

  4. Advanced Photon Source, Argonne National Laboratory, 9700 South Cass Avenue, Lemont, Illinois 60439, USA

    Yang Ren & Steve Wang

  5. Department of Materials Science and Engineering, Hanyang University, Seoul 133-791, South Korea

    Chong Seung Yoon

  6. Department and Institute of Nano Engineering, Sejong University, Seoul 143-747, South Korea

    Seung-Taek Myung

Authors
  1. Yang-Kook Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Zonghai Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hyung-Joo Noh
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Dong-Ju Lee
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Hun-Gi Jung
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yang Ren
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Steve Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Chong Seung Yoon
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Seung-Taek Myung
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Khalil Amine
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Y-K.S. and K.A. proposed the concept. Z.C., H-J.N., D-J.L., H-G.J., S-T.M., C.S.Y., Y.R. and S.W. performed the experiments and acquired the data. Y-K.S., Z.C. and K.A. wrote the paper.

Corresponding authors

Correspondence to Yang-Kook Sun or Zonghai Chen or Khalil Amine.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 2560 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Sun, YK., Chen, Z., Noh, HJ. et al. Nanostructured high-energy cathode materials for advanced lithium batteries. Nature Mater 11, 942–947 (2012). https://doi.org/10.1038/nmat3435

Download citation

Further reading

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing