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An efficient multi-doping strategy to enhance Li-ion conductivity in the garnet-type solid electrolyte Li7La3Zr2O12

Journal Article


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Abstract


  • Lithium-ion (Li + ) batteries suffer from problems caused by the chemical instability of their organic electrolytes. Solid-state electrolytes that exhibit high ionic conductivities and are stable to lithium metal are potential replacements for flammable organic electrolytes. Garnet-type Li 7 La 3 Zr 2 O 12 is a promising solid-state electrolyte for next-generation solid-state Li batteries. In this study, we prepared mono-, dual-, and ternary-doped lithium (Li) garnets by doping tantalum (Ta), tantalum-barium (Ta-Ba), and tantalum-barium-gallium (Ta-Ba-Ga) ions, along with an undoped Li 7 La 3 Zr 2 O 12 (LLZO) cubic garnet electrolyte, using a conventional solid-state reaction method. The effect of multi-ion doping on the Li + dynamics in the garnet-type LLZO was studied by combining joint Rietveld refinement against X-ray diffraction and high-resolution neutron powder diffraction analyses with the results of Raman spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and multinuclear magic angle spinning nuclear magnetic resonance. Our results revealed that Li + occupancy in the tetrahedrally coordinated site (24d) increased with increased multi-ion doping in LLZO, whereas Li + occupancy in the octahedrally coordinated site (96h) remained constant. Among the investigated compounds, the ternary-doped garnet structure Li 6.65 Ga 0.05 La 2.95 Ba 0.05 Zr 1.75 Ta 0.25 O 12 (LGLBZTO) exhibited the highest total ionic conductivity of 0.72 and 1.24 mS cm -1 at room temperature and 60 °C, respectively. Overall, our findings revealed that the dense microstructure and increased Li + occupancy in the tetrahedral-24d Li1 site played a key role in achieving the maximum room-temperature Li-ion conductivity in the ternary-doped LGLBZTO garnet, and that the prepared ternary-doped LGLBZTO was a potential solid electrolyte for Li-ion batteries without polymer adhesion.

Authors


  •   Meesala, Yedukondalu (external author)
  •   Liao, Yu-Kai (external author)
  •   Jena, Anirudha (external author)
  •   Yang, Nai-Hsuan (external author)
  •   Pang, Wei Kong.
  •   Hu, Shu-Fen (external author)
  •   Chang, Ho (external author)
  •   Liu, Chia-Erh (external author)
  •   Liao, Shih-Chieh (external author)
  •   Chen, Jin-Ming (external author)
  •   Guo, Xiangxin (external author)
  •   Liu, Ru-Shi (external author)

Publication Date


  • 2019

Citation


  • Meesala, Y., Liao, Y., Jena, A., Yang, N., Pang, W., Hu, S., Chang, H., Liu, C., Liao, S., Chen, J., Guo, X. & Liu, R. (2019). An efficient multi-doping strategy to enhance Li-ion conductivity in the garnet-type solid electrolyte Li7La3Zr2O12. Journal of Materials Chemistry A, 7 (14), 8589-8601.

Scopus Eid


  • 2-s2.0-85063944063

Ro Full-text Url


  • https://ro.uow.edu.au/cgi/viewcontent.cgi?article=4614&context=aiimpapers

Ro Metadata Url


  • http://ro.uow.edu.au/aiimpapers/3560

Number Of Pages


  • 12

Start Page


  • 8589

End Page


  • 8601

Volume


  • 7

Issue


  • 14

Place Of Publication


  • United Kingdom

Abstract


  • Lithium-ion (Li + ) batteries suffer from problems caused by the chemical instability of their organic electrolytes. Solid-state electrolytes that exhibit high ionic conductivities and are stable to lithium metal are potential replacements for flammable organic electrolytes. Garnet-type Li 7 La 3 Zr 2 O 12 is a promising solid-state electrolyte for next-generation solid-state Li batteries. In this study, we prepared mono-, dual-, and ternary-doped lithium (Li) garnets by doping tantalum (Ta), tantalum-barium (Ta-Ba), and tantalum-barium-gallium (Ta-Ba-Ga) ions, along with an undoped Li 7 La 3 Zr 2 O 12 (LLZO) cubic garnet electrolyte, using a conventional solid-state reaction method. The effect of multi-ion doping on the Li + dynamics in the garnet-type LLZO was studied by combining joint Rietveld refinement against X-ray diffraction and high-resolution neutron powder diffraction analyses with the results of Raman spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and multinuclear magic angle spinning nuclear magnetic resonance. Our results revealed that Li + occupancy in the tetrahedrally coordinated site (24d) increased with increased multi-ion doping in LLZO, whereas Li + occupancy in the octahedrally coordinated site (96h) remained constant. Among the investigated compounds, the ternary-doped garnet structure Li 6.65 Ga 0.05 La 2.95 Ba 0.05 Zr 1.75 Ta 0.25 O 12 (LGLBZTO) exhibited the highest total ionic conductivity of 0.72 and 1.24 mS cm -1 at room temperature and 60 °C, respectively. Overall, our findings revealed that the dense microstructure and increased Li + occupancy in the tetrahedral-24d Li1 site played a key role in achieving the maximum room-temperature Li-ion conductivity in the ternary-doped LGLBZTO garnet, and that the prepared ternary-doped LGLBZTO was a potential solid electrolyte for Li-ion batteries without polymer adhesion.

Authors


  •   Meesala, Yedukondalu (external author)
  •   Liao, Yu-Kai (external author)
  •   Jena, Anirudha (external author)
  •   Yang, Nai-Hsuan (external author)
  •   Pang, Wei Kong.
  •   Hu, Shu-Fen (external author)
  •   Chang, Ho (external author)
  •   Liu, Chia-Erh (external author)
  •   Liao, Shih-Chieh (external author)
  •   Chen, Jin-Ming (external author)
  •   Guo, Xiangxin (external author)
  •   Liu, Ru-Shi (external author)

Publication Date


  • 2019

Citation


  • Meesala, Y., Liao, Y., Jena, A., Yang, N., Pang, W., Hu, S., Chang, H., Liu, C., Liao, S., Chen, J., Guo, X. & Liu, R. (2019). An efficient multi-doping strategy to enhance Li-ion conductivity in the garnet-type solid electrolyte Li7La3Zr2O12. Journal of Materials Chemistry A, 7 (14), 8589-8601.

Scopus Eid


  • 2-s2.0-85063944063

Ro Full-text Url


  • https://ro.uow.edu.au/cgi/viewcontent.cgi?article=4614&context=aiimpapers

Ro Metadata Url


  • http://ro.uow.edu.au/aiimpapers/3560

Number Of Pages


  • 12

Start Page


  • 8589

End Page


  • 8601

Volume


  • 7

Issue


  • 14

Place Of Publication


  • United Kingdom