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The thermodynamic origin of hysteresis in insertion batteries

Nature Materials volume 9, pages 448–453 (2010)Cite this article

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Abstract

Lithium batteries are considered the key storage devices for most emerging green technologies such as wind and solar technologies or hybrid and plug-in electric vehicles. Despite the tremendous recent advances in battery research, surprisingly, several fundamental issues of increasing practical importance have not been adequately tackled. One such issue concerns the energy efficiency. Generally, charging of 1010–1017 electrode particles constituting a modern battery electrode proceeds at (much) higher voltages than discharging. Most importantly, the hysteresis between the charge and discharge voltage seems not to disappear as the charging/discharging current vanishes. Herein we present, for the first time, a general explanation of the occurrence of inherent hysteretic behaviour in insertion storage systems containing multiple particles. In a broader sense, the model also predicts the existence of apparent equilibria in battery electrodes, the sequential particle-by-particle charging/discharging mechanism and the disappearance of two-phase behaviour at special experimental conditions.

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Figure 1: Demonstration of the existence of a voltage gap at zero current for three different insertion battery materials.
Figure 2: Precise experiments showing the existence of a zero-current voltage gap in LiFePO4.
Figure 3: Comparison of chemical potential profiles in a single-particle and in a 10-particle system.
Figure 4: Two possible scenarios of new phase formation in a many-particle system.
Figure 5: Interpretation of voltage hysteresis in many-particle insertion systems with fast Li exchange between the particles and a non-monotone single-particle chemical potential.

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References

  1. Boyanov, S. et al. P-redox mechanism at the origin of the high lithium storage in NiP2-based batteries. Chem. Mater. 21, 298–308 (2009).

    Article  CAS  Google Scholar 

  2. Doe, R. E., Persson, K. A., Meng, Y. S. & Ceder, G. First-principles investigation of the Li–Fe–F phase diagram and equilibrium and nonequilibrium conversion reactions of iron fluorides with lithium. Chem. Mater. 20, 5274–5283 (2008).

    Article  CAS  Google Scholar 

  3. Ogasawara, T., Débart, A., Holzapfel, M., Novák, P. & Bruce, P. G. Rechargeable Li2O2 electrode for lithium batteries. J. Am. Chem. Soc. 128, 1390–1393 (2006).

    Article  CAS  Google Scholar 

  4. Yamada, A. et al. Room-temperature miscibility gap in LixFePO4 . Nature Mater. 5, 357–360 (2006).

    Article  CAS  Google Scholar 

  5. Dreyer, W., Guhlke, C. & Huth, R. The behaviour of a many particle cathode in a lithium-ion battery, WIAS Preprint No. 1423 (2009).

  6. Han, B. C., Van der Ven, A., Morgan, D. & Ceder, G. Electrochemical modeling of intercalation processes with phase field models. Electrochim. Acta 49, 4691–4699 (2004).

    Article  CAS  Google Scholar 

  7. Amin, R., Balaya, P. & Maier, J. Anisotropy of electronic and ionic transport in LiFePO4 single crystals. Electrochem. Solid State Lett. 10, A13–A16 (2007).

    Article  CAS  Google Scholar 

  8. Kang, B. & Ceder, G. Battery materials for ultrafast charging and discharging. Nature 458, 190–193 (2009).

    Article  CAS  Google Scholar 

  9. Srinivasan, V. & Newman, J. Discharge model for the lithium iron–phosphate electrode. J. Electrochem. Soc. 151, A1517–A1529 (2004).

    Article  CAS  Google Scholar 

  10. Srinivasan, V. & Newman, J. Existence of path-dependence in the LiFePO4 electrode. Electrochem. Solid State Lett. 9, A110–A114 (2006).

    Article  CAS  Google Scholar 

  11. Delmas, C., Maccario, M., Croguennec, L., Le Cras, F. & Weill, F. Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model. Nature Mater. 7, 665–671 (2008).

    Article  CAS  Google Scholar 

  12. Wagemaker, M., Borghols, W. J. H. & Mulder, F. M. Large impact of particle size on insertion reaction. A case for anatase LixTiO2 . J. Am. Chem. Soc. 129, 4323–4327 (2007).

    Article  CAS  Google Scholar 

  13. Hainovsky, N. & Maier, J. Simple phenomenological approach to premelting and sublattice melting in Frenkel disordered ionic crystals. Phys. Rev. B 51, 15789–15797 (1995).

    Article  CAS  Google Scholar 

  14. Müller, I. & Strehlow, P. Rubber and Rubber Balloons (Lecture Notes in Physics. Vol. 637, Springer, 2004).

    Book  Google Scholar 

  15. Gibot, P. et al. Room-temperature single-phase Li insertion/extraction in nanoscale LixFePO4 . Nature Mater. 7, 741–747 (2008).

    Article  CAS  Google Scholar 

  16. Dominko, R., Conte, R. D., Hanzel, D., Gaberscek, M. & Jamnik, J. Impact of synthesis conditions on the structure and performance of Li2FeSiO4 . J. Power Sources 178, 842–847 (2008).

    Article  CAS  Google Scholar 

  17. Erjavec, B. et al. Tailoring nanostructured TiO2 for high power Li-ion batteries. J. Power Sources 189, 869–874 (2009).

    Article  CAS  Google Scholar 

  18. Dominko, R. et al. Wired porous cathode materials: A novel concept for synthesis of LiFePO4 . Chem. Mater. 19, 2960–2969 (2007).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The main idea for this work was developed within the former ALISTORE Network of Excellence (now ALISTORE-ERI). The work has been partly supported by the Slovenian Research Agency (Grant No. P2-0148). Another part of the work was carried out as part of Project C26 ‘Storage of Hydrogen in Hydrides’ of the DFG research centre MATHEON, Berlin.

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Authors and Affiliations

  1. Weierstrass Institute for Applied Analysis and Stochastics, DE-10117 Berlin, Germany

    Wolfgang Dreyer, Clemens Guhlke & Robert Huth

  2. National Institute of Chemistry, Hajdrihova 19, SI-1000 Ljubljana, Slovenia

    Janko Jamnik, Jože Moškon & Miran Gaberšček

  3. Faculty of Chemistry and Chemical Technology, Aškerceva 5, SI-1000 Ljubljana, Slovenia

    Miran Gaberšček

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  1. Wolfgang Dreyer
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  2. Janko Jamnik
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  3. Clemens Guhlke
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  4. Robert Huth
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  5. Jože Moškon
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  6. Miran Gaberšček
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All authors contributed equally to this manuscript.

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Correspondence to Miran Gaberšček.

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Dreyer, W., Jamnik, J., Guhlke, C. et al. The thermodynamic origin of hysteresis in insertion batteries. Nature Mater 9, 448–453 (2010). https://doi.org/10.1038/nmat2730

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