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First-principles investigation of aluminum intercalation and diffusion in TiO2 materials: Anatase versus rutile

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journal contribution
posted on 02.07.2018 by Weiqiang Tang, Jin Xuan, Huizhi Wang, Shuangliang Zhao, Honglai Liu
Aluminum-ion batteries, emerging as a promising post-lithium battery solution, have been a subject of increasing research interest. Yet, most existing aluminum-ion research has focused on electrode materials development and synthesis. There has been a lack of fundamental understanding of the electrode processes and thus theoretical guidelines for electrode materials selection and design. In this study, by using density functional theory, we for the first time report a first-principles investigation on the thermodynamic and kinetic properties of aluminum intercalation into two common TiO 2 polymorphs, i.e., anatase and rutile. After examining the aluminum intercalation sites, intercalation voltages, storage capacities and aluminum diffusion paths in both cases, we demonstrate that the stable aluminum intercalation site locates at the center of the O 6 octahedral for TiO 2 rutile and off center for TiO 2 anatase. The maximum achievable Al/Ti ratios for rutile and anatase are 0.34375 and 0.36111, respectively. Although rutile is found to have an aluminum storage capacity slightly higher than anatase, the theoretical specific energy of rutile can reach 20.90 Wh kg −1 , nearly twice as high as anatase (9.84 Wh kg −1 ). Moreover, the diffusion coefficient of aluminum ions in rutile is 10 −9 cm 2 s −1 , significantly higher than that in anatase (10 −20 cm 2 s −1 ). In this regard, TiO 2 rutile appears to be a better candidate than anatase as an electrode material for aluminum-ion batteries.


This work is supported by National Natural Science Foundation of China (No. 91434110, U1707602), National Natural Science Foundation of China for Innovative Research Groups (No. 51621002), and the 111 Project of China (No.B08021). S.Z. acknowledges the support of Fok Ying Tong Education Foundation (151069) and W.T. is grateful to the China Scholarship Council and British Council for the visiting fellowship.



  • Aeronautical, Automotive, Chemical and Materials Engineering


  • Chemical Engineering

Published in

Journal of Power Sources




249 - 255


TANG, W. ... et al, 2018. First-principles investigation of aluminum intercalation and diffusion in TiO2 materials: Anatase versus rutile. Journal of Power Sources, 384, pp.249-255.


© Elsevier


AM (Accepted Manuscript)

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This work is made available according to the conditions of the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) licence. Full details of this licence are available at: https://creativecommons.org/licenses/by-nc-nd/4.0/

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This paper was published in the journal Journal of Power Sources and the definitive published version is available at https://doi.org/10.1016/j.jpowsour.2018.02.088.