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Post-doping via spray-drying: a novel sol–gel process for the batch synthesis of doped LiNi0.5Mn1.5O4 spinel material

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Abstract

Powder granulation, Ti-doping and thermal post-treatment have beneficial effects on the electrochemical performance of 5 V LiNi0.5Mn1.5O4 (LNMO) spinel materials. It is shown that spray-drying combined with a post-doping process step is suitable to prepare Ti-doped 5 V materials with a defined and highly reproducible microstructure and chemical composition. Powder granulation via spray-drying and thermal post-treatment provides spherical LNMO granules with nano-crystalline primary particles and a 10 % higher specific discharge capacity compared to pristine LNMO materials due to the presence of the partially ordered P4 3 32 spinel phase and the reduced Mn3+ content. Powder granulation combined with a post-doping process step which utilizes titanium containing sol leads to spherical LiNi0.5Mn1.47Ti0.03O4 granules with uniform nano-crystalline primary particles and a homogenous Ti distribution. The second calcination process after spray-drying as well as the Ti-doping cause a reduced content of the Li x Ni1−x O impurity phase. This facile sol–gel processing leads to doped LiNi0.5Mn1.47Ti0.03O4 with an increased discharge capacity of 18 % compared to the original material. All the granulated materials show a good rate performance up to 10 C due to their particular microstructure.

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Acknowledgements

The authors would like to thank the Federal Ministry of Education and Research (BMBF) and the Ministry of Science, Research and Arts Baden-Württemberg (MWK) for financial support. The authors are grateful for the invaluable support of this work by Florian Stemme (IAM-WPT, SEM images of the spinel powders) and Dr. Thomas Bergfeldt (IAM-AWP, extensive ICP analysis to reveal the exact chemical composition of the spinel materials). Finally the authors would like to acknowledge the help provided by Dr. Stephen Doyle during the data collection at ANKA PDIFF.

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Authors and Affiliations

  1. Institute for Applied Materials (IAM-WPT), Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany

    Melanie Schroeder, Sven Glatthaar, Holger Geßwein, Volker Winkler & Joachim R. Binder

  2. Institute for Applied Materials (IAM-ESS) Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany

    Volker Winkler & Michael Bruns

  3. Institute of Nanotechnology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany

    Torsten Scherer & Venkata Sai Kiran Chakravadhanula

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  1. Melanie Schroeder
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  2. Sven Glatthaar
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  3. Holger Geßwein
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  4. Volker Winkler
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  7. Venkata Sai Kiran Chakravadhanula
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  8. Joachim R. Binder
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Correspondence to Joachim R. Binder.

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Schroeder, M., Glatthaar, S., Geßwein, H. et al. Post-doping via spray-drying: a novel sol–gel process for the batch synthesis of doped LiNi0.5Mn1.5O4 spinel material. J Mater Sci 48, 3404–3414 (2013). https://doi.org/10.1007/s10853-012-7127-2

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  • DOI: https://doi.org/10.1007/s10853-012-7127-2

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