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Reversible magnesium and aluminium ions insertion in cation-deficient anatase TiO2

Nature Materials volume 16, pages 1142–1148 (2017)Cite this article

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Abstract

In contrast to monovalent lithium or sodium ions, the reversible insertion of multivalent ions such as Mg2+ and Al3+ into electrode materials remains an elusive goal. Here, we demonstrate a new strategy to achieve reversible Mg2+ and Al3+ insertion in anatase TiO2, achieved through aliovalent doping, to introduce a large number of titanium vacancies that act as intercalation sites. We present a broad range of experimental and theoretical characterizations that show a preferential insertion of multivalent ions into titanium vacancies, allowing a much greater capacity to be obtained compared to pure TiO2. This result highlights the possibility to use the chemistry of defects to unlock the electrochemical activity of known materials, providing a new strategy for the chemical design of materials for practical multivalent batteries.

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Figure 1: Titanium vacancies enabling insertion of Mg2+ and Al3+ in anatase.
Figure 2: Titanium vacancies enable reversible electrochemical magnesiation/alumination in anatase.
Figure 3: Ex situ structural analysis of magnesiated/de-magnesiated electrodes.
Figure 4: Chemical and local characterizations of Mg2+ in anatase.
Figure 5: Vacancy-mediated diffusion mechanism of Mg2+ in anatase.

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Acknowledgements

The research leading to these results has received funding from the French National Research Agency under Idex@Sorbonne University for the Future Investments programme (No. ANR-11-IDEX-0004-02) and by the German Federal Ministry of Education and Research (BMBF) through funding by the ‘Sino German TU9 network for electromobility’ under the grant reference number 16N11929. B.J.M. acknowledges support from the Royal Society (UF130329). This work made use of the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk), via the membership of the UK’s HPC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202). The work done at the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the US DOE under Contract No. DE-AC02-06CH11357. H.G. and D.D. wish to thank the French fluorine network for continuous support. M.B. and C.L. would like to thank C. Jacquemmoz (IMMM) for help with solid-state NMR experiments.

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Author notes

  1. Toshinari Koketsu and Jiwei Ma: These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Chemistry, Chemical Engineering Division, The Electrochemical Energy, Catalysis, and Materials Science Laboratory, Technical University Berlin, 10623 Berlin, Germany

    Toshinari Koketsu & Peter Strasser

  2. Sorbonne Universités, UPMC Univ Paris 06, CNRS UMR 8234, Laboratoire PHENIX, 4 place Jussieu, F-75005 Paris, France

    Jiwei Ma, Mathieu Salanne, François Dardoize, Henri Groult & Damien Dambournet

  3. Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS, 3459, France

    Jiwei Ma, Walid Dachraoui, Arnaud Demortière, Mathieu Salanne & Damien Dambournet

  4. Department of Chemistry, University of Bath, Bath BA2 7AY, UK

    Benjamin J. Morgan

  5. Université Bretagne Loire, Université du Maine, UMR CNRS 6283, Institut des Molécules et des Matériaux du Mans (IMMM), Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France

    Monique Body & Christophe Legein

  6. Laboratoire de Réactivité et Chimie des Solides, CNRS UMR 7314, Université de Picardie Jules Verne, 33 rue Saint Leu, 80039 Amiens Cedex, France

    Walid Dachraoui, Mattia Giannini & Arnaud Demortière

  7. ALISTORE-European Research Institute, FR CNRS 3104, 80039 Amiens, France

    Mattia Giannini & Arnaud Demortière

  8. Thermo Fisher Scientific, Materials and Structural Analysis, Achtseweg Noord 5, Eindhoven 5651 GG, The Netherlands

    Mattia Giannini

  9. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois, 60439, USA

    Olaf J. Borkiewicz & Karena W. Chapman

Authors
  1. Toshinari Koketsu
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Contributions

J.M., P.S. and D.D. conceived and coordinated the study. T.K., J.M., M.B., C.L., W.D., M.G., A.D., O.J.B., K.W.C., F.D., H.G., P.S. and D.D. carried out experimental work and data analysis. B.J.M. and M.S. conducted the computational study. All authors discussed the results and commented on the manuscript. J.M. and D.D. wrote the manuscript with the contributions of all co-authors.

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Correspondence to Jiwei Ma, Peter Strasser or Damien Dambournet.

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Koketsu, T., Ma, J., Morgan, B. et al. Reversible magnesium and aluminium ions insertion in cation-deficient anatase TiO2. Nature Mater 16, 1142–1148 (2017). https://doi.org/10.1038/nmat4976

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