Abstract

Phase transformations driven by compositional change require mass flux across a phase boundary. In some anisotropic solids, however, the phase boundary moves along a non-conductive crystallographic direction. One such material is LiXFePO4, an electrode for lithium-ion batteries. With poor bulk ionic transport along the direction of phase separation, it is unclear how lithium migrates during phase transformations. Here, we show that lithium migrates along the solid/liquid interface without leaving the particle, whereby charge carriers do not cross the double layer. X-ray diffraction and microscopy experiments as well as ab initio molecular dynamics simulations show that organic solvent and water molecules promote this surface ion diffusion, effectively rendering LiXFePO4 a three-dimensional lithium-ion conductor. Phase-field simulations capture the effects of surface diffusion on phase transformation. Lowering surface diffusivity is crucial towards supressing phase separation. This work establishes fluid-enhanced surface diffusion as a key dial for tuning phase transformation in anisotropic solids.

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References

  1. 1.

    Grey, C. P. & Tarascon, J. M. Sustainability and in situ monitoring in battery development. Nat. Mater. 16, 45–56 (2017).

  2. 2.

    Griessen, R., Strohfeldt, N. & Giessen, H. Thermodynamics of the hybrid interaction of hydrogen with palladium nanoparticles. Nat. Mater. 15, 311–317 (2016).

  3. 3.

    Trotochaud, L., Ranney, J. K., Williams, K. N. & Boettcher, S. W. Solution-cast metal oxide thin film electrocatalysts for oxygen evolution. J. Am. Chem. Soc. 134, 17253–17261 (2012).

  4. 4.

    Messerschmitt, F., Kubicek, M. & Rupp, J. L. M. How does moisture affect the physical property of memristance for anionic-electronic resistive switching memories? Adv. Funct. Mater. 25, 5117–5125 (2015).

  5. 5.

    Padhi, A. K., Nanjundaswamy, K. S. & Goodenough, J. B. Phospho-olivines as positive-electrode materials for rechargeable lithium batteries. J. Electrochem. Soc. 144, 1188–1194 (1997).

  6. 6.

    Delacourt, C., Poizot, P., Tarascon, J.-M. & Masquelier, C. The existence of a temperature-driven solid solution in LixFePO4 for 0 ≤ x ≤ 1. Nat. Mater. 4, 254–260 (2005).

  7. 7.

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

  8. 8.

    Tang, M., Carter, W. C. & Chiang, Y.-M. Electrochemically driven phase transitions in insertion electrodes for lithium-Ion batteries: examples in lithium metal phosphate olivines. Annu. Rev. Mater. Res. 40, 501–529 (2010).

  9. 9.

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

  10. 10.

    Morgan, D., Van der Ven, A. & Ceder, G. Li conductivity in LixMPO4 (M = Mn, Fe, Co, Ni) olivine materials. Electrochem. Solid State Lett. 7, A30–A32 (2004).

  11. 11.

    Islam, M. S., Driscoll, D. J., Fisher, C. A. J. & Slater, P. R. Atomic-scale investigation of defects, dopants, and lithium transport in the LiFePO4 olivine-type battery material. Chem. Mater. 17, 5085–5092 (2005).

  12. 12.

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

  13. 13.

    Dreyer, W. et al. The thermodynamic origin of hysteresis in insertion batteries. Nat. Mater. 9, 448–453 (2010).

  14. 14.

    Cogswell, D. A. & Bazant, M. Z. Coherency strain and the kinetics of phase separation in LiFePO4 nanoparticles. ACS Nano 6, 2215–2225 (2012).

  15. 15.

    Malik, R., Zhou, F. & Ceder, G. Kinetics of non-equilibrium lithium incorporation in LiFePO4. Nat. Mater. 10, 587–590 (2011).

  16. 16.

    Bai, P., Cogswell, D. A. & Bazant, M. Z. Suppression of phase separation in LiFePO4 nanoparticles during battery discharge. Nano Lett. 11, 4890–4896 (2011).

  17. 17.

    Orikasa, Y. et al. Direct observation of a metastable crystal phase of LixFePO4 under electrochemical phase transition. J. Am. Chem. Soc. 135, 5497–5500 (2013).

  18. 18.

    Zhang, X. et al. Rate-induced solubility and suppression of the first-order phase transition in olivine LiFePO4. Nano Lett. 14, 2279–2285 (2014).

  19. 19.

    Liu, H. et al. Capturing metastable structures during high-rate cycling of LiFePO4 nanoparticle electrodes. Science 344, 1252817 (2014).

  20. 20.

    Zhang, X. et al. Direct view on the phase evolution in individual LiFePO4 nanoparticles during Li-ion battery cycling. Nat. Commun. 6, 8333 (2015).

  21. 21.

    Lim, J. et al. Origin and hysteresis of lithium compositoinal spatiodynamics within battery primary particles. Science 353, 566–571 (2016).

  22. 22.

    Chen, G., Song, X. & Richardson, T. J. Electron microscopy study of the LiFePO4 to FePO4 phase transition. Electrochem. Solid State Lett. 9, A295–A298 (2006).

  23. 23.

    Yu, Y.-S. et al. Dependence on crystal size of the nanoscale chemical phase distribution and fracture in LixFePO4. Nano Lett. 15, 4282–4288 (2015).

  24. 24.

    Nishimura, S. et al. Experimental visualization of lithium diffusion in LixFePO4. Nat. Mater. 7, 707–711 (2008).

  25. 25.

    Malik, R., Burch, D., Bazant, M. & Ceder, G. Particle size dependence of the ionic diffusivity. Nano Lett. 10, 4123–4127 (2010).

  26. 26.

    Amin, R., Maier, J., Balaya, P., Chen, D. P. & Lin, C. T. Ionic and electronic transport in single crystalline LiFePO4 grown by optical floating zone technique. Solid State Ionics 179, 1683–1687 (2008).

  27. 27.

    Tealdi, C., Spreafico, C. & Mustarelli, P. Lithium diffusion in Li1–xFePO4: the effect of cationic disorder. J. Mater. Chem. 22, 24870–24876 (2012).

  28. 28.

    Hong, L. et al. Two-dimensional lithium diffusion behavior and probable hybrid phase transformation kinetics in olivine lithium iron phosphate. Nat. Commun. 8, 114 (2017).

  29. 29.

    Dathar, G. K. P., Sheppard, D., Stevenson, K. J. & Henkelman, G. Calculations of Li-ion diffusion in olivine phosphates. Chem. Mater. 23, 4032–4037 (2011).

  30. 30.

    Bazant, M. Z. Theory of chemical kinetics and charge transfer based on nonequilibrium thermodynamics. Acc. Chem. Res. 46, 1144–1160 (2013).

  31. 31.

    Marom, R., Haik, O., Aurbach, D. & Halalay, I. C. Revisiting LiClO4 as an electrolyte for rechargeable lithium-Ion batteries. J. Electrochem. Soc. 157, A972 (2010).

  32. 32.

    Li, Y. et al. Current-induced transition from particle-by-particle to concurrent intercalation in phase-separating battery electrodes. Nat. Mater. 13, 1149–1156 (2014).

  33. 33.

    Ferguson, T. R. & Bazant, M. Z. Nonequilibrium thermodynamics of porous electrodes. J. Electrochem. Soc. 159, A1967–A1985 (2012).

  34. 34.

    Koyama, Y. et al. Hidden two-step phase transition and competing reaction pathways in LiFePO4. Chem. Mater. 29, 2855–2863 (2017).

  35. 35.

    Benedek, R., Thackeray, M. M. & Van De Walle, A. Free energy for protonation reaction in lithium-ion battery cathode materials. Chem. Mater. 20, 5485–5490 (2008).

  36. 36.

    Luo, J.-Y., Cui, W.-J., He, P. & Xia, Y.-Y. Raising the cycling stability of aqueous lithium-ion batteries by eliminating oxygen in the electrolyte. Nat. Chem. 2, 760–765 (2010).

  37. 37.

    Zaghib, K. et al. Aging of LiFePO4 upon exposure to H2O. J. Power Sources 185, 698–710 (2008).

  38. 38.

    Cahn, J. W. On spinodal decomposition. Acta Metall. 9, 795–801 (1961).

  39. 39.

    Fisher, C. A. J. & Islam, M. S. Surface structures and crystal morphologies of LiFePO4: relevance to electrochemical behaviour. J. Mater. Chem. 18, 1209–1215 (2008).

  40. 40.

    Zaghib, K., Mauger, A., Gendron, F. & Julien, C. M. Surface effects on the physical and electrochemical properties of thin LiFePO4 particles. Chem. Mater. 20, 462–469 (2008).

  41. 41.

    Rho, Y., Nazar, L. F., Perry, L. & Ryan, D. Surface chemistry of LiFePO4 studied by Mössbauer and X-ray photoelectron spectroscopy and its effect on electrochemical properties. J. Electrochem. Soc. 154, A283–A289 (2007).

  42. 42.

    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).

  43. 43.

    Cogswell, D. A. & Bazant, M. Z. Theory of coherent nucleation in phase-separating nanoparticles. Nano Lett. 13, 3036–3041 (2013).

  44. 44.

    Ferguson, T. R. & Bazant, M. Z. Phase transformation dynamics in porous battery electrodes. Electrochim. Acta 146, 89–97 (2014).

  45. 45.

    Bazant, M. Z. Thermodynamic stability of driven open systems and control of phase separation by electroautocatalysis. Faraday Discuss. 199, 423–463 (2017).

  46. 46.

    Woodford, W. H., Carter, W. C. & Chiang, Y.-M. Design criteria for electrochemical shock resistant battery electrodes. Energy Environ. Sci. 5, 8014–8024 (2012).

  47. 47.

    Katsman, A., Beregovsky, M. & Yaish, Y. E. Formation and evolution of nickel silicide in silicon nanowires. IEEE Trans. Electron Devices 61, 3363–3371 (2014).

  48. 48.

    Wang, H., Yuan, H., Hong, S. S., Li, Y. & Cui, Y. Physical and chemical tuning of two-dimensional transition metal dichalcogenides. Chem. Soc. Rev. 44, 2664–2680 (2014).

  49. 49.

    Anasori, B., Lukatskaya, M. & Gogotsi, Y. 2D metal carbides and nitrides (MXenes) for energy storage. Nat. Rev. Mater. 2, 16098 (2017).

  50. 50.

    Tao, X. et al. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design. Nat. Commun. 7, 11203 (2016).

  51. 51.

    Nelson Weker, J., Li, Y., Shanmugam, R., Lai, W. & Chueh, W. C. Tracking non-uniform mesoscale transport in LiFePO4 agglomerates during electrochemical cycling. ChemElectroChem 2, 1576–1581 (2015).

  52. 52.

    Islam, M. S. & Fisher, C. A. J. Lithium and sodium battery cathode materials: computational insights into voltage, diffusion and nanostructural properties. Chem. Soc. Rev. 43, 185–204 (2014).

  53. 53.

    Ceder, G. Opportunities and challenges for first-principles materials design and applications to Li battery materials. MRS Bull. 35, 693–702 (2010).

  54. 54.

    Meng, Y. S. & Dompablo, M. E. A. Computational research of cathode materials for lithium-ion batteries. Acc. Chem. Res. 46, 1171–1180 (2013).

  55. 55.

    Kresse, G. & Furthmu, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

  56. 56.

    Perdew, J. P. et al. Restoring the density-gradient expansion for exchange in solids and surfaces. Phys. Rev. Lett. 100, 136406 (2008).

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Acknowledgements

This experimental work at Stanford and SLAC was supported by the US Department of Energy (DOE), Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under contract DE-AC02-76SF00515. Phase-field theoretical work at MIT and Stanford was supported by the Toyota Research Institute through D3BATT: Center for Data-Driven Design of Li-Ion Batteries. The Advanced Light Source and the Stanford Synchrotron Radiation Lightsource are supported by the DOE Office of Basic Energy Sciences under contracts DE-AC02-05CH11231 and DE-AC02-76SF00515. M.S.I. and H.C. acknowledge support from the EPSRC (grant EP/K016288) and the Archer HPC facilities through the Materials Chemistry Consortium (EP/L000202). Y.L. and P.M.A. were supported by the NSF Graduate Research Fellowship under grant DGE-114747. K.L. was supported by the Kwanjeong Education Foundation Fellowship. M.Z.B. was supported by the Global Climate and Energy Project at Stanford University and the DOE Office of Basic Energy Sciences through the SUNCAT Center for Interface Science and Catalysis. Part of this work was conducted the Stanford Nano Shared Facilities. We thank W. D. Nix (Stanford) for insightful discussions on metallurgy and mechanical properties and R. B. Smith (MIT) for assistance with the phase-field model. We also thank A. L. D. Kilcoyne (Berkeley) and D. Shaprio (Berkeley) for assistance with synchrotron measurements.

Author information

Author notes

    • Yiyang Li

    Present address: Sandia National Laboratories, Livermore, CA, USA

Affiliations

  1. Department of Materials Science & Engineering, Stanford University, Stanford, CA, USA

    • Yiyang Li
    • , Kipil Lim
    • , Haitao D. Deng
    • , Jongwoo Lim
    • , Peter M. Attia
    • , Sang Chul Lee
    • , Norman Jin
    • , Jihyun Hong
    • , Martin Z. Bazant
    •  & William C. Chueh
  2. Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    • Yiyang Li
    • , Jongwoo Lim
    •  & William C. Chueh
  3. Department of Chemistry, University of Bath, Bath, UK

    • Hungru Chen
    •  & M. Saiful Islam
  4. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    • Kipil Lim
    •  & Jihyun Hong
  5. Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

    • Dimitrios Fraggedakis
    •  & Martin Z. Bazant
  6. National Institute of Chemistry, Ljubljana, Slovenia

    • Jože Moškon
    •  & Miran Gaberšček
  7. Department of Applied Physics, Stanford University, Stanford, CA, USA

    • Zixuan Guan
  8. Department of Chemistry, Stanford University, Stanford, CA, USA

    • William E. Gent
  9. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    • Young-Sang Yu
  10. Faculty of Chemistry and Chemical Technology, University of Ljubljana, Ljubljana, Slovenia

    • Miran Gaberšček
  11. Department of Mathematics, Massachusetts Institute of Technology, Cambridge, MA, USA

    • Martin Z. Bazant
  12. SUNCAT Interfacial Science and Catalysis, Stanford University, Stanford, CA, USA

    • Martin Z. Bazant

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Contributions

Y.L. conceived and designed the project, analysed the experimental data and performed the phase-field simulations. H.C. and M.S.I. conducted the molecular dynamics simulations. Y.L., K.L. and J.H. conducted diffraction. Y.L., J.L., P.M.A., N.J., W.E.G. and Y.S.Y. collected the X-ray microscopy images. S.C.L. performed transmission electron microscopy. D.F., Y.L. and M.Z.B. designed and executed the linear stability analysis. H.D.D., J.M. and M.G. quantified the resistance increase during relaxation. M.S.I. supervised the molecular dynamics simulations. M.Z.B. supervised the phase-field simulations and linear stability analysis. W.C.C. supervised the experimental components of the work. All authors contributed to writing the text.

Competing interests

The authors declare no competing interests.

Corresponding authors

Correspondence to M. Saiful Islam or Martin Z. Bazant or William C. Chueh.

Supplementary information

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    Supplementary Figures 1–17, Supplementary Table 1, Supplementary References

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https://doi.org/10.1038/s41563-018-0168-4