Abstract
Lithium-ion batteries are a key technology for multiple clean energy applications. Their energy and power density is largely determined by the cathode materials, which store Li by incorporation into their crystal structure. Most commercialized cathode materials, such as LiCoO2 (ref. 1), LiMn2O4 (ref. 2), Li(Ni,Co,Al)O2 or Li(Ni,Co,Mn)O2 (ref. 3), form solid solutions over a large concentration range, with occasional weak first-order transitions as a result of ordering1 of Li or electronic effects4. An exception is LiFePO4, which stores Li through a two-phase transformation between FePO4 and LiFePO4 (refs 5, 6, 7, 8). Notwithstanding having to overcome extra kinetic barriers, such as nucleation of the second phase and growth through interface motion, the observed rate capability of LiFePO4 has become remarkably high9,10,11. In particular, once transport limitations at the electrode level are removed through carbon addition and particle size reduction, the innate rate capability of LiFePO4 is revealed to be very high. We demonstrate that the reason LiFePO4 functions as a cathode at reasonable rate is the availability of a single-phase transformation path at very low overpotential, allowing the system to bypass nucleation and growth of a second phase. The LixFePO4 system is an example where the kinetic transformation path between LiFePO4 and FePO4 is fundamentally different from the path deduced from its equilibrium phase diagram.
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References
Reimers, J. N. & Dahn, J. R. Electrochemical and in situ X-ray-diffraction studies of lithium intercalation in LixCoO2 . J. Electrochem. Soc. 139, 2091–2097 (1992).
Thackeray, M. M., Johnson, P. J., Depicciotto, L. A., Bruce, P. G. & Goodenough, J. B. Electrochemical extraction of lithium from LiMn2O4 . Mater. Res. Bull. 19, 179–187 (1984).
Ohzuku, T. & Makimura, Y. Layered lithium insertion material of LiCo1/3Ni1/3Mn1/3O2 for lithium-ion batteries. Chem. Lett. 30, 642–643 (2001).
Menetrier, M., Saadoune, I., Levasseur, S. & Delmas, C. The insulator–metal transition upon lithium deintercalation from LiCoO2: Electronic properties and Li-7 NMR study. J. Mater. Chem. 9, 1135–1140 (1999).
Delacourt, C., Poizot, P., Tarascon, J. M. & Masquelier, C. The existence of a temperature-driven solid solution in LixFePO4 for 0<=x<=1. Nature Mater. 4, 254–260 (2005).
Dodd, J. L., Yazami, R. & Fultz, B. Phase diagram of Li(x)FePO4 . Electrochem. Solid State Lett. 9, A151–A155 (2006).
Zhou, F., Maxisch, T. & Ceder, G. Configurational electronic entropy and the phase diagram of mixed-valence oxides: The case of LixFePO4 . Phys. Rev. Lett. 97, 155704 (2006).
Yamada, A. et al. Room-temperature miscibility gap in LixFePO4 . Nature Mater. 5, 357–360 (2006).
Chung, S. Y., Bloking, J. T. & Chiang, Y. M. Electronically conductive phospho-olivines as lithium storage electrodes. Nature Mater. 1, 123–128 (2002).
Kang, B. & Ceder, G. Battery materials for ultrafast charging and discharging. Nature 458, 190–193 (2009).
Kim, D. H. & Kim, J. Synthesis of LiFePO4 nanoparticles in polyol medium and their electrochemical properties. Electrochem. Solid State Lett. 9, A439–A442 (2006).
Allen, J. L., Jow, T. R. & Wolfenstine, J. Kinetic study of the electrochemical FePO4 to LiFePO4 phase transition. Chem. Mater. 19, 2108–2111 (2007).
Padhi, A., Nanjundaswamy, K. & Goodenough, J. Phospho-olivines as positive-electrode materials for rechargeable lithium batteries. J. Electrochem. Soc. 144, 1188–1194 (1997).
Srinivasan, V. & Newman, J. Discharge model for the lithium iron-phosphate electrode. J. Electrochem. Soc. 151, A1517–A1529 (2004).
Wang, C., Kasavajjula, U. S. & Arce, P. E. A discharge model for phase transformation electrodes: Formulation, experimental validation, and analysis. J. Phys. Chem. C 111, 16656–16663 (2007).
Laffont, L. et al. Study of the LiFePO4/FePO4 two-phase system by high-resolution electron energy loss spectroscopy. Chem. Mater. 18, 5520–5529 (2006).
Chen, G. Y., Song, X. Y. & Richardson, T. J. Electron microscopy study of the LiFePO4 to FePO4 phase transition. Electrochem. Solid State Lett. 9, A295–A298 (2006).
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).
Porter, D. A. & Easterling, K. E. Phase Transformations in Metals and Alloys 2nd edn (CRC, 2004).
Wagemaker, M., Mulder, F. M. & Van der Ven, A. The role of surface and interface energy on phase stability of nanosized insertion compounds. Adv. Mater. 21, 2703–2709 (2009).
Van der Ven, A., Garikipati, K., Kim, S. & Wagemaker, M. The role of coherency strains on phase stability in LixFePO4: Needle crystallites minimize coherency strain and overpotential. J. Electrochem. Soc. 156, A949–A957 (2009).
Dreyer, W. et al. The thermodynamic origin of hysteresis in insertion batteries. Nature Mater. 9, 448–453 (2010).
Zhou, F., Cococcioni, M., Kang, K. & Ceder, G. The Li intercalation potential of LiMPO4 and LiMSiO4 olivines with M=Fe, Mn, Co, Ni. Electrochem. Commun. 6, 1144–1148 (2004).
Gu, L. et al. Direct observation of lithium staging in partially delithiated LiFePO4 at atomic resolution. J. Am. Chem. Soc. 133, 4661–4663 (2011).
Morgan, D., Van der Ven, A. & Ceder, G. Li conductivity in LixMPO (M=Mn, Fe, Co, Ni) olivine materials. Electrochem. Solid State Lett. 7, A30–A32 (2004).
Delacourt, C., Rodriguez-Carvajal, J., Schmitt, B., Tarascon, J. M. & Masquelier, C. Crystal chemistry of the olivine-type LixFePO4 system (0<=x<=1) between 25 and 370 °C. Solid State Sci. 7, 1506–1516 (2005).
Chen, G., Song, X. & Richardson, T. J. Metastable solid-solution phases in the LiFePO4/FePO4 system. J. Electrochem. Soc. 154, A627–A632 (2007).
Dodd, J., Yazami, R. & Fultz, B. Phase diagram of Li(x)FePO4 . Electrochem. Solid State 9, A151–A155 (2006).
Chang, H. H. et al. Study on dynamics of structural transformation during charge/discharge of LiFePO4 cathode. Electrochem. Commun. 10, 335–339 (2008).
Dominko, R., Conte, D. E., Hanzel, D., Gaberscek, M. & Jamnik, J. Impact of synthesis conditions on the structure and performance of Li2FeSiO4 . J. Power Sources 178, 842–847 (2008).
Acknowledgements
This work was supported as part of the Northeastern Center for Chemical Energy Storage, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001294. The electronic structure work enabling this work was funded by the Department of Energy, Office of Basic Energy Science, Grant No. DE-FG02-96ER4557. The authors thank the National Partnership for Advanced Computing Infrastructure (NPACI) for computational resources. The authors would like to acknowledge A. Abdellahi, M. Z. Bazant, C. P. Grey and A. Van der Ven for their helpful discussions and comments.
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R.M. and G.C. developed the model and wrote the manuscript. R.M. performed Monte Carlo simulations. F.Z. performed DFT calculations.
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Malik, R., Zhou, F. & Ceder, G. Kinetics of non-equilibrium lithium incorporation in LiFePO4. Nature Mater 10, 587–590 (2011). https://doi.org/10.1038/nmat3065
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DOI: https://doi.org/10.1038/nmat3065
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