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Experimental visualization of lithium diffusion in LixFePO4


Chemical energy storage using batteries will become increasingly important for future environmentally friendly (‘green’) societies. The lithium-ion battery is the most advanced energy storage system, but its application has been limited to portable electronics devices owing to cost and safety issues1. State-of-the-art LiFePO4 technology as a new cathode material with surprisingly high charge–discharge rate capability has opened the door for large-scale application of lithium-ion batteries such as in plug-in hybrid vehicles2,3,4,5. The scientific community has raised the important question of why a facile redox reaction is possible in the insulating material6,7,8,9,10,11,12,13,14. Geometric information on lithium diffusion is essential to understand the facile electrode reaction of LixFePO4 (0<x<1), but previous approaches have been limited to computational predictions15,16. Here, we provide long-awaited experimental evidence for a curved one-dimensional chain for lithium motion. By combining high-temperature powder neutron diffraction and the maximum entropy method, lithium distribution along the [010] direction was clearly visualized.

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Figure 1: Crystal structure of LiFePO4 and possible lithium pathways.
Figure 2: Neutron diffraction patterns measured at two specific points in the FePO4–LiFePO4 binary phase diagram.
Figure 3: Anisotropic harmonic lithium vibration in LiFePO4 shown as green thermal ellipsoids and the expected diffusion path.
Figure 4: Nuclear distribution of lithium calculated by the MEM using neutron powder diffraction data measured for Li0.6FePO4 at 620 K.


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The authors would like to thank Y. Yamaguchi, M. Yonemura, H. Koizumi and K. Nemoto for their support in the neutron diffraction experiments. This work was financially supported by the Ministry of Education, Culture, Sports, Science and Technology of Japan, through a Grant-in-Aid for Scientific Research (A) No. 19205027, and the New Energy and Industrial Technology Development Organization (NEDO). JSPS fellowship No. 19.10259 is greatly appreciated by S.N.

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Authors and Affiliations



S.N. carried out sample preparation, room-temperature neutron diffraction experiments at VEGA, structure analysis, MEM analysis and all of the related work in supporting information, G.K. carried out sample preparation and the high-temperature neutron diffraction (HT-ND) experiments at HERMES, K.O. set up the equipment for the HT-ND experiments at HERMES, R.K. co-supervised the project, M.Y. supervised the HT-ND experiments at HERMES, A.Y. conceived, supervised and coordinated the whole project. S.N. and A.Y. wrote the manuscript.

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Correspondence to Atsuo Yamada.

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Supplementary Figures S1–S6 and Tables S1 & S2 (PDF 3334 kb)

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Nishimura, Si., Kobayashi, G., Ohoyama, K. et al. Experimental visualization of lithium diffusion in LixFePO4. Nature Mater 7, 707–711 (2008).

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