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Revealing lithium–silicide phase transformations in nano-structured silicon-based lithium ion batteries via in situ NMR spectroscopy

Author

Listed:
  • K. Ogata

    (University of Cambridge)

  • E. Salager

    (University of Cambridge
    Present address: CNRS, UPR3079 CEMHTI, 1D avenue de la recherche scientifique, 45071 Orléans Cedex 2, France)

  • C.J. Kerr

    (University of Cambridge)

  • A.E. Fraser

    (University of Cambridge)

  • C. Ducati

    (University of Cambridge)

  • A.J. Morris

    (Cavendish Laboratory, University of Cambridge)

  • S. Hofmann

    (University of Cambridge)

  • C.P. Grey

    (University of Cambridge
    Stony Brook University)

Abstract

Nano-structured silicon anodes are attractive alternatives to graphitic carbons in rechargeable Li-ion batteries, owing to their extremely high capacities. Despite their advantages, numerous issues remain to be addressed, the most basic being to understand the complex kinetics and thermodynamics that control the reactions and structural rearrangements. Elucidating this necessitates real-time in situ metrologies, which are highly challenging, if the whole electrode structure is studied at an atomistic level for multiple cycles under realistic cycling conditions. Here we report that Si nanowires grown on a conducting carbon-fibre support provide a robust model battery system that can be studied by 7Li in situ NMR spectroscopy. The method allows the (de)alloying reactions of the amorphous silicides to be followed in the 2nd cycle and beyond. In combination with density-functional theory calculations, the results provide insight into the amorphous and amorphous-to-crystalline lithium–silicide transformations, particularly those at low voltages, which are highly relevant to practical cycling strategies.

Suggested Citation

  • K. Ogata & E. Salager & C.J. Kerr & A.E. Fraser & C. Ducati & A.J. Morris & S. Hofmann & C.P. Grey, 2014. "Revealing lithium–silicide phase transformations in nano-structured silicon-based lithium ion batteries via in situ NMR spectroscopy," Nature Communications, Nature, vol. 5(1), pages 1-11, May.
  • Handle: RePEc:nat:natcom:v:5:y:2014:i:1:d:10.1038_ncomms4217
    DOI: 10.1038/ncomms4217
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    Cited by:

    1. Jack E. N. Swallow & Michael W. Fraser & Nis-Julian H. Kneusels & Jodie F. Charlton & Christopher G. Sole & Conor M. E. Phelan & Erik Björklund & Peter Bencok & Carlos Escudero & Virginia Pérez-Dieste, 2022. "Revealing solid electrolyte interphase formation through interface-sensitive Operando X-ray absorption spectroscopy," Nature Communications, Nature, vol. 13(1), pages 1-14, December.
    2. Lyu, Chao & Song, Yankong & Zheng, Jun & Luo, Weilin & Hinds, Gareth & Li, Junfu & Wang, Lixin, 2019. "In situ monitoring of lithium-ion battery degradation using an electrochemical model," Applied Energy, Elsevier, vol. 250(C), pages 685-696.

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