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Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries

Abstract

Rechargeable solid-state batteries have long been considered an attractive power source for a wide variety of applications, and in particular, lithium-ion batteries are emerging as the technology of choice for portable electronics. One of the main challenges in the design of these batteries is to ensure that the electrodes maintain their integrity over many discharge–recharge cycles. Although promising electrode systems have recently been proposed1,2,3,4,5,6,7, their lifespans are limited by Li-alloying agglomeration8 or the growth of passivation layers9, which prevent the fully reversible insertion of Li ions into the negative electrodes. Here we report that electrodes made of nanoparticles of transition-metal oxides (MO, where M is Co, Ni, Cu or Fe) demonstrate electrochemical capacities of 700 mA h g-1, with 100% capacity retention for up to 100 cycles and high recharging rates. The mechanism of Li reactivity differs from the classical Li insertion/deinsertion or Li-alloying processes, and involves the formation and decomposition of Li2O, accompanying the reduction and oxidation of metal nanoparticles (in the range 1–5 nanometres) respectively. We expect that the use of transition-metal nanoparticles to enhance surface electrochemical reactivity will lead to further improvements in the performance of lithium-ion batteries.

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Figure 1: Properties of MO/Li cells.
Figure 2: In situ X-ray diffraction patterns collected at various states of discharge and charge of a CoO/Li electrochemical cell.
Figure 3: TEM images and SAED patterns of CoO electrodes taken from non-cycled, fully discharged and fully charged cells.
Figure 4: Capacity fading of Cu2O-based electrodes as a function of the particle size.

References

  1. 1

    Shodai, T., Okada, S., Tobishima, S. & Yamabi, J. Study of Li 3-xMxN (M = Co, Ni or Cu) system for use as anode in lithium rechargeable cells. Solid State Ionics 786, 86–88 (1996).

    Google Scholar 

  2. 2

    Takeda, Y. et al. Lithium secondary batteries using a lithium cobalt nitride, Li 2.6Co0.4N, as the anode. Solid State Ionics 130, 61–69 (2000).

    CAS  Article  Google Scholar 

  3. 3

    Idota, Y., Kubota, T., Matsufuji, A., MaeKawa, Y. & Miyasaka, T. Tin-based amorphous oxide: A high-capacity lithium-ion storage material. Science 276, 1395–1397 (1997).

    CAS  Article  Google Scholar 

  4. 4

    Kepler, K. D., Vaughey, J. T. & Thackeray, M. M. LixCu6Sn5 (0<x<13): An intermetallic insertion electrode for rechargeable lithium batteries. Electrochem. Solid State Lett. 7, 307– 309 (1999).

    Article  Google Scholar 

  5. 5

    Mao, O., Dunlap, R. A. & Dahn, J. R. Mechanically alloyed Sn-Fe(-C) powders as anode materials for Li-ion batteries. I. The Sn2Fe-C system. J. Electrochem. Soc. 146, 405–413 ( 1999).

    CAS  Article  Google Scholar 

  6. 6

    Idota, Y. et al. Nonaqueous secondary battery. US Patent No. 5,478,671 (1995).

  7. 7

    Sigala, C., Guyomard, D., Piffard, Y. & Tournoux, M. Synthesis and performances of new negative electrode materials for ‘Rocking Chair’ lithium batteries. C.R. Acad. Sci. Paris II 320, 523–529 (1995).

    CAS  Google Scholar 

  8. 8

    Courtney, I. A., McKinnon, W. R. & Dahn, J. R. On the aggregation of tin in SnO composite glasses caused by the reversible reaction with lithium. J. Electrochem. Soc. 146, 59–68 ( 1999).

    CAS  Article  Google Scholar 

  9. 9

    Denis, S., Baudrin, E., Touboul, M. & Tarascon, J.-M. Synthesis and electrochemical properties vs Li of amorphous vanadates of general formula RVO4 (R = In, Cr, Al, Fe, Y). J. Electrochem. Soc. 144, 4099–4109 (1997).

    CAS  Article  Google Scholar 

  10. 10

    Guyomard, D. & Tarascon, J.-M. Rechargeable Li1+xMn 2O4/carbon cells with a new electrolyte composition. Potentiostatic studies and application to practical cells. J. Electrochem. Soc. 140, 3071–3081 ( 1993).

    CAS  Article  Google Scholar 

  11. 11

    Gozdz, A. S., Tarascon, J.-M. & Schmutz, C. N. Rechargeable lithium interaction battery with flexible electrolyte. US Patent No. 5,296,318 (1994).

  12. 12

    Amatucci, G. G., Tarascon, J.-M. & Klein, L. C. CoO2, the end member of the LixCoO 2 solid solution. J. Electrochem. Soc. 143 , 1114–1123 (1996).

    CAS  Article  Google Scholar 

  13. 13

    Figlarz, M., Fievet, F. & Lagier, J.-P. Reduction process of metal-based inorganic precursors in liquid polyols to produce monodisperse metal particles. French patent No. 8,221,483 (1985).

  14. 14

    Buffat, P. & Borel, J. P. Size effect on the melting temperature of gold particles. Phys. Rev. A 13, 2287 –2292 (1976).

    ADS  CAS  Article  Google Scholar 

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Acknowledgements

We thank E. Baudrin, D. Larcher, M. Morcrette, Y. Chabre, G. Amatucci and C. Masquelier for discussions.

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Correspondence to J-M. Tarascon.

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Poizot, P., Laruelle, S., Grugeon, S. et al. Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries. Nature 407, 496–499 (2000). https://doi.org/10.1038/35035045

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