Abstract
With respect to lithium batteries, vanadate-based electrodes display large electrochemical capacities that rapidly decay during the cycling. A full study of the 3d-metal(M)-based vanadates performed using in situ DRX, XAS and TEM has enabled to pinpoint the important role of the 3d-metal cations, and has motivated the study of simple metal oxides MO, (M=Co, Ni, Cu, Fe) in rechargeable Li cells. We found that these materials could reversibly react with a large amount of lithium leading to capacities as high as 800 mAh/g. The reactivity mechanism totally differs from the well established one based on Li insertion-deinsertion or Li alloying reactions but mainly involves the formation of highly reactive metallic nanoparticles that favor Li2O formation-decomposition. Besides, we gave experimental evidence of an electrochemically driven polymerization-dissolution process at low potential, which is highly reversible, and emphasized the importance of the role of the electrolyte on such a process. Finally, the universality of this mechanism to account for the large Li reactivity at low voltage in many 3d-metal (Co, Ni, Fe, Cu, Mn)-based oxides is discusséd together with the urgent issues to be solved for such oxide anodes to stand as serious alternative candidates for today’s carbon anodes in Li-ion cells.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
6. Reference
T. Shodai, S. Okada, S. Tobishima and J. Yamabi, Solid State Ionics786, 86 (1996).
M. Hasegawa, J. Yamaura and S. Tsutsumi, Fall ECS Meeting Abstract, Hawai, No 174, 1999.
Y. Idota, T. Kubota, A. Matsufuji, Y. Maekawa and T. Miyasaka, Science276, 1395 (1997).
I.A. Courtney and J.R. Dahn, J. Electrochem. Soc.144, 2045 (1999).
T. Brousse, R. Retoux, U. Herterich and D.M. Schleich, J. Electrochem. Soc.145, 1 (1998).
K.D. Kepler, J.T. Vaughey and M.M. Thackeray, Electrochem. Solid-State Lett.7, 307 (1999).
O. Mao and J.R. Dahn, J. Electrochem. Soc.146, 414 (1999);146, 423 (1999).
I. Yoshio, European Patent No 0567749 AI (1993).
C. Sigala, D. Guyomard, Y. Piffard, M. Tournoux and C.R. Acad. Sci., Série II, 523 (1995).
F. Orsini, E. Baudrin, S. Denis, L. Dupont, M. Touboul, D. Guyomard, Y. Piffard and J.-M. Tarascon, Solid State Ionics107, 123 (1998).
S. Denis, E. Baudrin, M. Touboul, J.-M. Tarascon, J. Electrochem. Soc.144, 4099 (1997).
S. Denis, F. Orsini, M. Touboul and J.-M. Tarascon, US Patent No 5 700 598.
E. Baudrin, S. Laruelle, S. Denis, M. Touboul and J.-M. Tarascon, Solid State Ionics123, 139 (1999).
P. Poizot, S. Laruelle, S. Grugeon, L. Dupont and J.-M. Tarascon, Paper presented at IMLB-10 conference on Li Batteries, Como, Italy (2000). To be published in Journal of Power Sources.
P. Poizot, S. Laruelle, S. Grugeon, L. Dupont, B. Beaudoin and J.-M. Tarascon, C. R. Acad. Sci., Série IIc, 3, 681 (2000).
P. Poizot, S. Laruelle, S. Grugeon, L. Dupont and J.-M. Tarascon, Nature407, 496 (2000).
S. Grugeon, S. Laruelle, R. Herera-Urbina, L. Dupont, P. Poizot and J.-M. Tarascon, to be published in the Journal of the Electrochemical Society.
P. Poizot, S. Laruelle, B. Beaudoin, M. Touboul and J.-M. Tarascon. Solid State Ionics138, 31 (2000).
E. Baudrin, S. Denis, F. Orsini, L. Seguin, M. Touboul and J.-M. Tarascon, J. Mater. Chem.9, 101 (1999).
J.-M. Tarascon, A.S. Gozdz, C. Schmutz, F. Shokoohi and P.C. Warren, Solid State Ionics86, 49 (1996).
S. Denis, E. Baudrin, F. Orsini, G. Ouvrard, M. Touboul and J.-M. Tarascon, J. Power Sources79, 81 (1999).
S. Denis, R. Dedryvère, J.-C. Jumas, M. Touboul and J.-M. Tarascon, Chem. Mat. (in press).
S. Laruelle, P. Poizot, E. Baudrin, V. Briois, M. Touboul and J.-M. Tarascon, J. Power Sources (submitted).
C. Delmas, J.-M. Cocciantelli, M. Ménétrier and J.P. Doumerc, Solid State Ionics69, 257 (1994).
S. Geniès, R. Yazami, J. Garden and J.C. Frisson, Synth. Metals93, 77 (1998).
M. Dollé, S. Grugeon, B. Beaudoin, L. Dupont and J.-M. Tarascon, J. Power Sources (submitted).
M.M. Thackeray, W.I.F. David and J.B. Goodenough, J. Solid State Chem.55, 280 (1984).
M.M. Thackeray, Handbook of Battery Materials, Wiley-VCH, Weinheim, 1999, p. 307.
I.A. Courtney, R.A. Dunlap and J.R. Dahn, Electrochimica Acta.45, 51 (1999).
O.W. Smith, J. Chem. Educ.64, 480 (1987).
O. Kubaschewski and C.B. Alcock, Metallurgical Thermochemistry, 5th edition, Pergamon press.
D. Aurbach, B. Markousky, A. Schechter and Y. Ein-Eli, J. Electrochem. Soc.143, 3809 (1996).
D. Aurbach, M.D. Levi, E. Levi and A. Schechter, J. Phys. Chem. B101, 2195 (1997).
T. Li, P.B. Balbuena, Chem. Phys. Lett.317, 421 (2000).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Poizot, P., Laruelle, S., Grugeon, S. et al. From the vanadates to 3d-metal oxides negative electrodes. Ionics 6, 321–330 (2000). https://doi.org/10.1007/BF02374148
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF02374148