The DOI matches its Crossref record; 17 of the 17 references it cites were found in a registry or an index.
Two Phase Morphology Limits Lithium Diffusion in TiO2 (Anatase): A 7Li MAS NMR Study
Abstract
7Li magic angle spinning solid-state nuclear magnetic resonance is applied to investigate the lithium local environment and lithium ion mobility in tetragonal anatase TiO(2) and orthorhombic lithium titanate Li(0.6)TiO(2). Upon lithium insertion, an increasing fraction of the material changes its crystallographic structure from anatase TiO(2) to lithium titanate Li(0.6)TiO(2). Phase separation occurs, and as a result, the Li-rich lithium titanate phase is coexisting with the Li-poor TiO(2) phase containing only small Li amounts approximately equal to 0.01. In both the anatase and the lithium titanate lattice, Li is found to be hopping over the available sites with activation energies of 0.2 and 0.09 eV, respectively. This leads to rapid microscopic diffusion rates at room temperature (D(micr) = 4.7 x 10(-12) cm(2)s(-1) in anatase and D(micr) = 1.3 x 10(-11) cm(2)s(-1) in lithium titanate). However, macroscopic intercalation data show activation energies of approximately 0.5 eV and smaller diffusion coefficients. We suggest that the diffusion through the phase boundary is determining the activation energy of the overall diffusion and the overall diffusion rate itself. The chemical shift of lithium in anatase is independent of temperature up to approximately 250 K but decreases at higher temperatures, reflecting a change in the 3d conduction electron densities. The Li mobility becomes prominent from this same temperature showing that such electronic effects possibly facilitate the mobility.
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Citations
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Cited by
Xie, Y., Naguib, M., Mochalin, V. N., Barsoum, M. W., Gogotsi, Y., Yu, X., Nam, K.-W., Yang, X.-Q., Kolesnikov, A. I., & Kent, P. R. C. (2014) · Journal of the American Chemical Society · doi:10.1021/ja501520b · Cited by 1,537
Green energy storage materials: Nanostructured TiO2 and Sn-based anodes for lithium-ion batteries
Deng, D., Kim, M. G., Lee, J. Y., & Cho, J. (2009) · Energy & Environmental Science · doi:10.1039/b823474d · Cited by 891
Joo, J., Kwon, S. G., Yu, T., Cho, M., Lee, J., Yoon, J., & Hyeon, T. (2005) · The Journal of Physical Chemistry B · doi:10.1021/jp052458z · Cited by 386
Waldmann, T., Iturrondobeitia, A., Kasper, M., Ghanbari, N., Aguesse, F., Bekaert, E., Daniel, L., Genies, S., Gordon, I. J., Löble, M. W., et al. (2016) · Journal of The Electrochemical Society · doi:10.1149/2.1211609jes · Cited by 328
An Ultrafast, Energy‐Efficient Electrochromic and Thermochromic Device for Smart Windows
Deng, B., Zhu, Y., Wang, X., Zhu, J., Liu, M., Liu, M., He, Y., Zhu, C., Zhang, C., & Meng, H. (2023) · Advanced Materials · doi:10.1002/adma.202302685 · Cited by 259
Metadata
- Authors
- Wagemaker, M., van de Krol, R., Kentgens, A. P. M., van Well, A. A., & Mulder, F. M.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2001-10-18
- Volume
- 123
- Issue
- 46
- Pages
- 11454-11461
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W1979620931
- Cited by
- 306
- References
- 17
- FWCI
- 5.44
- Type
- journal article
- Language
- en
- Open access
- closed
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