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

Weiqiang Tang, Jin Xuan, Huizhi Wang*, Shuangliang Zhao, Honglai Liu

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

28 Citations (Scopus)


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 TiO2 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 O6 octahedral for TiO2 rutile and off center for TiO2 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 cm2 s−1, significantly higher than that in anatase (10−20 cm2 s−1). In this regard, TiO2 rutile appears to be a better candidate than anatase as an electrode material for aluminum-ion batteries.

Original languageEnglish
Pages (from-to)249-255
Number of pages7
JournalJournal of Power Sources
Early online date23 Mar 2018
Publication statusPublished - 30 Apr 2018


  • Aluminum-ion batteries
  • First-principles calculations
  • Intercalation mechanisms
  • Mesoscale
  • Titanium dioxide electrode

ASJC Scopus subject areas

  • Renewable Energy, Sustainability and the Environment
  • Energy Engineering and Power Technology
  • Physical and Theoretical Chemistry
  • Electrical and Electronic Engineering


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