Revealing lithium–silicide phase transformations in nano-structured silicon-based lithium ion batteries via in situ NMR spectroscopy
- 3 February 2014
- journal article
- research article
- Published by Springer Nature in Nature Communications
- Vol. 5 (1) , 1-11
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.Keywords
This publication has 51 references indexed in Scilit:
- In Situ TEM Investigation of Congruent Phase Transition and Structural Evolution of Nanostructured Silicon/Carbon Anode for Lithium Ion BatteriesNano Letters, 2012
- Fracture of crystalline silicon nanopillars during electrochemical lithium insertionProceedings of the National Academy of Sciences, 2012
- Concurrent Reaction and Plasticity during Initial Lithiation of Crystalline Silicon in Lithium-Ion BatteriesJournal of the Electrochemical Society, 2012
- Pair Distribution Function Analysis and Solid State NMR Studies of Silicon Electrodes for Lithium Ion Batteries: Understanding the (De)lithiation MechanismsJournal of the American Chemical Society, 2010
- Si nanoparticle-decorated Si nanowire networks for Li-ion battery anodesChemical Communications, 2010
- High-performance lithium-ion anodes using a hierarchical bottom-up approachNature Materials, 2010
- Crystalline-Amorphous Core−Shell Silicon Nanowires for High Capacity and High Current Battery ElectrodesNano Letters, 2009
- Silicon Composite Electrode with High Capacity and Long Cycle LifeElectrochemical and Solid-State Letters, 2009
- Reversible Cycling of Crystalline Silicon PowderJournal of the Electrochemical Society, 2007
- In Situ XRD and Electrochemical Study of the Reaction of Lithium with Amorphous SiliconJournal of the Electrochemical Society, 2004