Synthesis and ionic conductivity of Li₆La₃BiSnO₁₂ with cubic garnet-type structure via solid-state reaction

Abstract

The synthesis and transport properties of the Li₆La₃BiSnO₁₂ solid electrolyte by a solid-state reaction were reported. The condition to synthesize the Li₆La₃BiSnO₁₂ is 785 °C for 36 h in air. The refined lattice constant of Li₆La₃BiSnO₁₂ is 13.007 Å. Qualitative phase analysis by X-ray powder diffraction patterns combined with the Rietveld method reveals garnet type compounds as major phases. The Li-ion conductivity of the prepared Li₆La₃BiSnO₁₂ is 0.85×10^–4 S/cm at 22 °C, which is comparable with that of the Li₅La₃Bi₂O₁₂. The Li₆La₃BiSnO₁₂ compounds are chemically stable against LiCoO₂ which is widely used as cathode material up to 700 °C but not against the LiMn₂O₄ if the temperature is higher than 550 °C. The Li₆La₃BiSnO₁₂ exhibits higher chemical stability than Li₅La₃Bi₂O₁₂, which is due to Sn substitution for Bi.

Keywords

Li⁺-ion solid electrolyte / lithium battery / garnet-type electrolyte / solid-state reaction

References

[1] KotobukiM, SuzukiY, KanamuraK, SatoY, YamamotoK, YoshidaT. A novel structure of ceramics electrolyte for future lithium battery [J]. Journal of Power Sources, 2011, 196(22): 9815-9831

[2] KiyoharuT, RyoheiT, TakahiroI, ShigeoM, AkitoshiH, MasahiroT. Low temperature synthesis of highly ion conductive Li₇La₃Zr₂O₁₂-Li₃BO₃ composites [J]. Electrochemistry Communications, 2013, 33(1): 51-54

[3] MasashiK, MasakiK. Preparation of Li_1.5Al_0.5Ti_1.5(PO₄)₃ solid electrolyte via a solgel route using various Al sources [J]. Ceramics International, 2013, 39(11): 4645-4649

[4] PengH-j, XieH, GoodenoughJ B. Use of B₂O₃ to improve Li⁺-ion transport in LiTi₂(PO₄)₃-based ceramics [J]. Journal of Power Sources, 2012, 197(2): 310-313

[5] ThangaduraiV, AdamsS, WeppnerW. Crystal structure revision and identification of Li⁺-ion migration pathways in the garnet-like Li₅La₃M₂O₁₂ (M= Nb, Ta) oxides [J]. Chem Mater, 2004, 35(41): 2998-3006

[6] ThangduraiV, KaackH, WeppnerW. Novel fast lithium ion conduction in garnet-type Li₅La₃M₂O₁₂ (M=Nb, Ta) [J]. J Am Ceram Soc, 2003, 86(3): 437-440

[7] MuruganR, WeppnerW, Schmid-BeurmannP, ThangaduraiV. Structure and lithium ion conductivity of bismuth containing lithium garnets Li₅La₃Bi₂O₁₂ and Li₆SrLa₂Bi₂O₁₂ [J]. Materials Science and Engineering B, 2007, 143: 14-20

[8] GaoY X, WangX P, WangW G, ZhuangZ, ZhangD M, FangQ F. Synthesis ionic conductivity and chemical compatibility of garnet-like lithium ionic conductor Li₅La₃Bi₂O₁₂ [J]. Solid State Ionics, 2010, 181(7): 1415-1419

[9] ThangaduraiV, WeppnerW. Li₆ALa₂Nb₂O₁₂ (A=Ca, Sr, Ba): A new class of fast lithium ion conductors with garnet-like structure [J]. J Am Ceram Soc, 2005, 88(2): 411-418

[10] ThangaduraiV, WeppnerW. Li₆ALa₂Ta₂O₁₂ (A=Sr, Ba): Novel garnet-like oxides for fast lithium ion conduction [J]. Advance Functional Materials, 2005, 15(1): 107-112

[11] ThangaduraiV, WeppnerW. Investigations on electrical conductivity and chemical compatibility between fast lithium ion conducting garnet-like Li₆BaLa₂Ta₂O₁₂ and lithium battery cathodes [J]. Journal of Power Sources, 2005, 142: 339-344

[12] FuL J, LiuH, LiC, WuY P, RahmE, HolzeR, WuH Q. Electrode materials for lithium secondary batteries prepared by sol–gel methods [J]. Prog Mater Sci, 2005, 50(2): 881-928

[13] MoonH S, LeeS W, LeeY K. Characterization of protectivelayer-coated LiMn₂O₄ cathode thin films [J]. Journal of Power Sources, 2003, 119: 713-716

[14] ArumugamD, KalaignanG P. Synthesis and electrochemical characterization of nano-CeO₂-coated nanostructure LiMn₂O₄ cathode materials for rechargeable lithium batteries [J]. Electrochimica Acta, 2010, 55(28): 8709-8716