Influence of particle size, cycling rate and temperature on the lithiation process of anatase TiO2
Journal of Materials Chemistry A
Royal Society of Chemistry
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Liu, H., & Grey, C. (2016). Influence of particle size, cycling rate and temperature on the lithiation process of anatase TiO2. Journal of Materials Chemistry A https://doi.org/10.1039/C6TA00673F
The nature of a phase transition plays an important role in controlling the kinetics of reaction of an electrode material in a lithium-ion battery. The actual phase transition path can be affected by particle size and cycling rate. In this study, we investigated the phase transition process during the electrochemical Li intercalation of anatase TiO2 as a function of particle size (25 nm and 100 nm), cycling rate (1C, 2C, 5C, 10C, 20C) and temperature (room temperature and 80 deg C) by in situ synchrotron X-ray diffraction. The phase transition was found to be affected by the particle size: the 100 nm particles react simultaneously via a conventional nucleation and growth, i.e. two-phase, mechanism, while the 25 nm particles react sequentially via a two-phase mechanism. The Li miscibility gap decreases with increasing cycling rate, yet the phase separation was not suppressed even at a cycle rate of 20C. An increase in temperature from room temperature to 80 deg C significantly improves the electrode's electrochemical performance despite undergoing a two-phase reaction. The failure to observe a continuous structural transition from tetragonal TiO2 to orthorhombic Li0.5TiO2 even at high rates and elevated temperature was attributed to the high energy barrier of a continuous phase transition path.
This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This work was supported by funding from European Union FP7- 265368 via the Eurolion Project and the Cambridge Overseas Trust (materials preparation, XRD), and as part of the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Awards DE-SC0012583 (data analysis). We thank Dr Tao Liu for help with the SEM, Dr Simon Clarke and Dr Michael Carpenter for their helpful comments and discussions, and Dr Kamila Wiaderek, Dr Olaf Borkiewicz, Dr Karena Chapman and Dr Peter Chupas for their help with the setup for XRD measurement.
EC FP7 CP (NMP3-SL-2010-265368)
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External DOI: https://doi.org/10.1039/C6TA00673F
This record's URL: https://www.repository.cam.ac.uk/handle/1810/255713
Attribution 4.0 International
Licence URL: http://creativecommons.org/licenses/by/4.0/
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