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Title: Influence of particle size, cycling rate and temperature on the lithiation process of anatase TiO2

Journal Article · · Journal of Materials Chemistry. A
DOI:https://doi.org/10.1039/c6ta00673f· OSTI ID:1326101
 [1];  [1]
  1. Univ. of Cambridge (United Kingdom)

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 °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 °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.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); European Union (EU); Cambridge Overseas Trust
Grant/Contract Number:
AC02-06CH11357; SC0012583
OSTI ID:
1326101
Journal Information:
Journal of Materials Chemistry. A, Vol. 4, Issue 17; ISSN 2050-7488
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
ENGLISH
Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

References (18)

Capturing metastable structures during high-rate cycling of LiFePO4 nanoparticle electrodes journal June 2014
Kinetics of Anatase Electrodes: The Role of Ordering, Anisotropy, and Shape Memory Effects journal July 2012
Multiple Li Positions inside Oxygen Octahedra in Lithiated TiO 2 Anatase journal January 2003
Nonequilibrium Structural Dynamics of Nanoparticles in LiNi 1/2 Mn 3/2 O 4 Cathode under Operando Conditions journal August 2014
Electrochemical Performance of Anatase Nanotubes Converted from Protonated Titanate Hydrate Nanotubes journal January 2005
Constructing Hierarchical Spheres from Large Ultrathin Anatase TiO 2 Nanosheets with Nearly 100% Exposed (001) Facets for Fast Reversible Lithium Storage journal May 2010
The electronic structure and ionic diffusion of nanoscale LiTiO2 anatase journal January 2009
Impact of Particle Size on the Non-Equilibrium Phase Transition of Lithium-Inserted Anatase TiO 2 journal February 2014
Application of symmetrized harmonics expansion to correction of the preferred orientation effect journal August 1993
Two Phase Morphology Limits Lithium Diffusion in TiO 2 (Anatase):  A 7 Li MAS NMR Study journal November 2001
The AMPIX electrochemical cell: a versatile apparatus for in situ X-ray scattering and spectroscopic measurements journal November 2012
Ternary LixTiO2 phases from insertion reactions journal December 1983
Kinetics of non-equilibrium lithium incorporation in LiFePO4 journal July 2011
Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model journal July 2008
Suppression of Phase Separation in LiFePO 4 Nanoparticles During Battery Discharge journal November 2011
Rate-Induced Solubility and Suppression of the First-Order Phase Transition in Olivine LiFePO 4 journal April 2014
Large Impact of Particle Size on Insertion Reactions. A Case for Anatase Li x TiO 2 journal April 2007
Electrochemistry of anatase titanium dioxide in lithium nonaqueous cells journal January 1985

Cited By (1)