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Synthesis of lithium conducting titanium phosphates by the sol-gel process

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Abstract

The synthesis of titanium and lithium phosphates was studied using the sol-gel method. Particular attention was paid to phosphate precursors, which were mixtures of phosphate mono- and diesters prepared by solvolysis of P4O10 in isopropanol. The reaction of these precursors with titanium and lithium alkoxides yielded homogeneous gels and after drying and thermal cleavage of the esters at 300 °C, amorphous inorganic products. For the composition corresponding to the stoichiometric formula of a stable compound such as LiTi2(PO4)3, the phase crystallized as early as 550 °C by nucleation from the amorphous mixture. Ionic conductivity measured at room temperature was of the order of 10−5 S·cm−1 which increased after heat treatment at higher temperatures. If the composition did not correspond to a stable thermodynamic phase, phase separation occurred, and ionic conductivity decreased between 500 °C and 700 °C.

Graphical Abstract

Highlights

  • Lithium solid electrolyte LiTi2(PO4)3 was synthesized by sol-gel reaction.

  • Control of the reaction was performed by thermal cleavage of phosphate esters.

  • Same method was used to screen new lithium-titanium-phosphate compositions.

  • Lithium-ion conductivity was measured.

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Acknowledgements

NMR equipment at ESPCI Paris PSL is funded in part by the Paris Region. We thank Agence Nationale de la Recherche et de la Technologie for the financial support of A. Guillot during thesis contract CIFRE n°2020/1330.

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Authors and Affiliations

  1. Chimie Paristech, PSL Research University, CNRS, Institut de Recherche de Chimie Paris (IRCP), 75005, Paris, France

    A. Guillot, D. Giaume, A. Suvorova & P. Barboux

  2. Ampere, Battery Chemistry Research, Technocentre Renault, Guyancourt, France

    A. Guillot, C. Mir & X. Randrema

  3. Réseau sur le stockage électrochimique de l’énergie (rs2e), Amiens, CNRS 3459, France

    D. Giaume & P. Barboux

  4. Chimie Paristech, PSL Research University, NMR Facility, Paris, France

    M. N. Rager

  5. ESPCI Paris PSL, PSL Research University, Sorbonne Université, CNRS, Soft Matter Science and Engineering, Paris, France

    J.-B. d’Espinose de Lacaillerie

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  1. A. Guillot
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  2. D. Giaume
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  3. A. Suvorova
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  5. J.-B. d’Espinose de Lacaillerie
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  6. C. Mir
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  8. P. Barboux
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Contributions

AG performed the synthesis characterization during his PhD work, helped by AS during her master’s internship. MNR performed the liquid-state NMR characterizations at Chimie Paristech and J-BD the solid-state NMR experiments at ESPCI. CM and XR supervised the work on the industrial site while DG and PB supervised the PhD and academic work. AG and PB prepared the figures. PB, AG, and DG wrote the main manuscript text. All authors reviewed the document.

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Correspondence to P. Barboux.

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Guillot, A., Giaume, D., Suvorova, A. et al. Synthesis of lithium conducting titanium phosphates by the sol-gel process. J Sol-Gel Sci Technol (2024). https://doi.org/10.1007/s10971-024-06461-2

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