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Multiphase transformation and Ostwald’s rule of stages during crystallization of a metal phosphate

Nature Physics volume 5, pages 68–73 (2009)Cite this article

Abstract

Although the classical picture of crystallization depicts a simple and immediate transformation from an amorphous to a crystalline phase, it has been argued that, in selected systems, intermediate metastable phases exist before a stable state is finally reached. However, most experimental observations have been limited to colloids and proteins, for which the crystallization kinetics are fairly slow and the size is comparatively large. Here, we demonstrate for the first time in an inorganic compound at an atomic scale that an amorphous phase transforms into a stable crystalline state via intermediate crystalline phases, thus directly proving Ostwald’s rule of stages. Through in situ high-resolution electron microscopy in real time at a high temperature, we show the presence of metastable transient phases at an atomic scale during the crystallization of an olivine-type metal phosphate. These results suggest a new description for the kinetic pathway of crystallization in complex inorganic systems.

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Figure 1: First series of in situ HREM images and corresponding FFTs during the crystallization of LiFePO4 at 450 ∘C.
Figure 2: Second series of in situ HREM images and corresponding FFTs of a LiFePO4 nanocrystal at 450 ∘C.
Figure 3: Atomic potential contour maps calculated by crystallographic image processing.
Figure 4: Third series of in situ HREM images of a LiFePO4 nanocrystal at 450 ∘C.
Figure 5: Extra series of in situ HREM images of another LiFePO4 nanocrystal at 450 ∘C.
Figure 6: Schematic diagram showing the transition pathway during the crystallization of LiFePO4.

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Acknowledgements

This work was supported by the Korea Research Foundation, grant no. 2007-331-D00196.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, Inha University, Incheon 402-751, Korea

    Sung-Yoon Chung

  2. Nalphates LLC, Wilmington, Delaware 19801, USA

    Sung-Yoon Chung

  3. Korea Basic Science Institute, Daejeon 305-333, Korea

    Young-Min Kim, Jin-Gyu Kim & Youn-Joong Kim

Authors
  1. Sung-Yoon Chung
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Contributions

S.-Y.C. conceived, designed and carried out the experiments, analysed the data, interpreted and discussed the results and wrote the paper. Y.-M.K., J.-G.K. and Y.-J.K. provided the TEM facilities and contributed the acquisition of TEM data.

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Correspondence to Sung-Yoon Chung.

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Chung, SY., Kim, YM., Kim, JG. et al. Multiphase transformation and Ostwald’s rule of stages during crystallization of a metal phosphate. Nature Phys 5, 68–73 (2009). https://doi.org/10.1038/nphys1148

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