DOI QR코드

DOI QR Code

Preparation and Characterization of Ta-substituted Li7La3Zr2-xO12 Garnet Solid Electrolyte by Sol-Gel Processing

  • Yoon, Sang A (Department of Advanced Materials Engineering, Korea Polytechnic University) ;
  • Oh, Nu Ri (Department of Advanced Materials Engineering, Korea Polytechnic University) ;
  • Yoo, Ae Ri (Department of Advanced Materials Engineering, Korea Polytechnic University) ;
  • Lee, Hee Gyun (Department of Advanced Materials Engineering, Korea Polytechnic University) ;
  • Lee, Hee Chul (Department of Advanced Materials Engineering, Korea Polytechnic University)
  • Received : 2017.04.10
  • Accepted : 2017.06.19
  • Published : 2017.07.31

Abstract

In this work, Ta-substituted $Li_7La_3Zr_{2-x}O_{12}$ (LLZTO) powder and pellets with garnet cubic structure were fabricated and characterized by modified and optimized sol-gel synthesis. Ta-substituted LLZO powder with the smallest grain size and pure cubic structure with little pyrochlore phase was obtained by synthesis method in which Li and La sources in propanol solvent were mixed together with Zr and Ta sources in 2-methoxy ethanol. The LLZTO pellets made with the prepared powder showed cubic garnet structure for all conditions when the amount of Li addition was varied from 6.2 to 7.4 mol. All the X-ray peaks of the pyrochlore phase disappeared when the Li addition was increased above 7.0 mol. When the final sintering temperature was varied, the LLZTO pellet had a pyrochlore-mixed cubic phase above $1000^{\circ}C$. However, the surface morphology became much denser when the final sintering temperature was increased. The sol-gel-driven LLZTO pellet with a sintering temperature of $1100^{\circ}C$ showed a lithium ionic conductivity of 0.21 mS/cm when Au was adopted as electrode material for the blocking capacitor. The results of this study suggest that modified sol-gel synthesis is the optimum method to obtain cubic phase of LLZTO powder for highly dense and conductive solid electrolyte ceramics.

Keywords

References

  1. K. B. Dermenci, E. Cekic, and S. Turan, "Al Stabilized $Li_7La_3Zr_2O_{12}$ Solid Electrolytes for All-Solid State Li-Ion Batteries," Int. J. Hydrogen Energy, 41 [23] 9860-67 (2016). https://doi.org/10.1016/j.ijhydene.2016.03.197
  2. Y. Zhang, J. Cai, F. Chen, R. Tu, Q. Shen, X. Zhang, and L. Zhang, "Preparation of Cubic $Li_7La_3Zr_2O_{12}$ Solid Electrolyte Using a Nano-Sized Core-Shell Structured Precursor," J. Alloys Compd., 644 793-98 (2015). https://doi.org/10.1016/j.jallcom.2015.05.085
  3. J. Wolfenstine, E. Rangasamy, J. L. Allen, and J. Sakamoto, "High Conductivity of Dense Tetragonal $Li_7La_3Zr_2O_{12}$," J. Power Sources, 208 193-96 (2012). https://doi.org/10.1016/j.jpowsour.2012.02.031
  4. Y. Zhang, F. Chen, R. Tu, Q. Shen, and L. Zhang, "Field Assisted Sintering of Dense Al-Substituted Cubic Phase $Li_7La_3Zr_2O_{12}$ Solid Electrolytes," J. Power Sources, 268 960-64 (2014). https://doi.org/10.1016/j.jpowsour.2014.03.148
  5. J. Wolfenstine, J. Ratchford, E. Rangasamy, J. Sakamoto, and J. L. Allen, "Synthesis and High Li-Ion Conductivity of Ga-Stabilized Cubic $Li_7La_3Zr_2O_{12}$," Mater. Chem. Phys., 134 [2] 571-75 (2012). https://doi.org/10.1016/j.matchemphys.2012.03.054
  6. E. J. Cussen, "Structure and Ionic Conductivity in Lithium Garnets," J. Mater. Chem., 20 [25] 5167-73 (2010). https://doi.org/10.1039/b925553b
  7. I. Quinzeni, D. Capsoni, V. Berbenni, P. Mustarelli, M. Sturini, and M. Bini, "Stability of Low-Temperature $Li_7La_3Zr_2O_{12}$ Cubic Phase: The Role of Temperature and Atmosphere," Mater. Chem. Phys., 185 55-64 (2017). https://doi.org/10.1016/j.matchemphys.2016.10.004
  8. J. Awaka, N. Kijima, H. Hayakawa, and J. Akimoto, "Synthesis and Structure Analysis of Tetragonal $Li_7La_3Zr_2O_{12}$ with the Garnet-Related Type Structure," J. Solid State Chem., 182 [8] 2046-52 (2009). https://doi.org/10.1016/j.jssc.2009.05.020
  9. K. Liu, J. T. Ma, and C. A. Wang, "Excess Lithium Salt Functions More than Compensating for Lithium Loss when Synthesizing $Li_{6.5}La_3Ta_{0.3}Zr_{1.5}O_{12}$ in Alumina Crucible," J. Power Sources, 260 109-14 (2014). https://doi.org/10.1016/j.jpowsour.2014.02.065
  10. T. Liu, Y. Ren, Y. Shen, S. X. Zhao, Y. Lin, and C. W. Nan, "Achieving High Capacity in Bulk-Type Solid-State Lithium Ion Battery Based on $Li_{6.75}La_3Zr_{1.75}Ta_{0.25}O_{12}$ Electrolyte: Interfacial Resistance," J. Power Sources, 324 349-57 (2016). https://doi.org/10.1016/j.jpowsour.2016.05.111
  11. K. C. Santosh, C. L. Roberto, K. Xiong, and K. Cho, "Point Defects in Garnet-Type Solid Electrolyte (c-$Li_7La_3Zr_2O_{12}$) for Li-Ion Batteries," Solid State Ionics, 261 100-5 (2014). https://doi.org/10.1016/j.ssi.2014.04.021
  12. K. Tadanaga, N. C. Rosero-Navarro, T. Yamashita, A. Miura, and M. Higuchi, "Preparation of $Li_7La_3(Zr_{2-x},Nb_x)O_{12}$ (x = 0 - 1.5) and $Li_3BO_3/LiBO_2$ Composites at Low Temperatures Using a Sol-Gel Process," Solid State Ionics, 285 6-12 (2016). https://doi.org/10.1016/j.ssi.2015.06.015
  13. A. R. Yoo, S. A. Yoon, Y. S. Kim, J. Sakamoto, and H. C. Lee, "A Comparative Study on the Synthesis of Al-Doped $Li_{6.2}La_3Zr_2O_{12}$ Powder as a Solid Electrolyte Using Sol-Gel Synthesis and Solid-State Processing," J. Nanosci. Nanotechnol., 16 [11] 11662-68 (2016). https://doi.org/10.1166/jnn.2016.13570
  14. N. Rosenkiewitz, J. Schuhmacher, M. Bockmeyer, and J. Deubener, "Nitrogen-Free Sol-Gel Synthesis of Al-Substituted Cubic Garnet $Li_7La_3Zr_2O_{12}$ (LLZO)," J. Power Sources, 278 104-8 (2015). https://doi.org/10.1016/j.jpowsour.2014.12.066
  15. E. Rangasamy, J. Wolfenstine, J. Allen, and J. Sakamoto, "The Effect of 24c-site (A) Cation Substitution on the Tetragonal-Cubic Phase Transition in $Li_{7-x}La_{3-x}A_xZr_2O_{12}$ Garnet-Based Ceramic Electrolyte," J. Power Sources, 230 261-66 (2013). https://doi.org/10.1016/j.jpowsour.2012.12.076
  16. T. Thompson, J. Wolfenstine, J. L. Allen, M. Johannes, A. Huq, I. N. David, and J. Sakamoto, "Tetragonal vs. Cubic Phase Stability in Al-Free Ta Doped $Li_7La_3Zr_2O_{12}$ (LLZO)," J. Mater. Chem. A, 2 [33] 13431-36 (2014). https://doi.org/10.1039/C4TA02099E
  17. J. Sakamoto, E. Rangasamy, H. Kim, Y. Kim, and J. Wolfenstine, "Synthesis of Nano-Scale Fast Ion Conducting Cubic $Li_7La_3Zr_2O_{12}$," Nanotechnology, 24 [42] 424005-12 (2013). https://doi.org/10.1088/0957-4484/24/42/424005
  18. I. Kokal, M. Somer, P. H. L. Notten, and H. T. Hintzen, "Sol-Gel Synthesis and Lithium Ion Conductivity of $Li_7La_3Zr_2O_{12}$ with Garnet-Related Type Structure," Solid State Ionics, 185 [1] 42-6 (2011). https://doi.org/10.1016/j.ssi.2011.01.002
  19. N. Janani, S. Ramakumar, S. Kannan, and R. Murugan, "Optimization of Lithium Content and Sintering Aid for Maximized $Li^+$ Conductivity and Density in Ta-doped $Li_7La_3Zr_2O_{12}$," J. Am. Ceram. Soc., 98 [7] 2039-46 (2015). https://doi.org/10.1111/jace.13578

Cited by

  1. Enhanced Cathode/Sulfide Electrolyte Interface Stability Using an Li2ZrO3 Coating for All-Solid-State Batteries vol.9, pp.3, 2017, https://doi.org/10.5229/jecst.2018.9.3.176
  2. Preparation of high density garnet electrolytes by impregnation sintering for lithium-ion batteries vol.30, pp.8, 2017, https://doi.org/10.1007/s10854-019-01131-4
  3. Nonaqueous Polymer Combustion Synthesis of Cubic Li7La3Zr2O12 Nanopowders vol.12, pp.1, 2017, https://doi.org/10.1021/acsami.9b19981
  4. Reduction in Formation Temperature of Ta-Doped Lithium Lanthanum Zirconate by Application of Lux-Flood Basic Molten Salt Synthesis vol.3, pp.7, 2017, https://doi.org/10.1021/acsaem.0c00716
  5. Highly Conductive Garnet-Type Electrolytes: Access to Li6.5La3Zr1.5Ta0.5O12 Prepared by Molten Salt and Solid-State Methods vol.12, pp.43, 2017, https://doi.org/10.1021/acsami.0c14056
  6. Effects of alkaline earth metal elements and their synergistic roles with Ta for Li7La3Zr2O12 vol.7, pp.12, 2017, https://doi.org/10.1088/2053-1591/abcc85
  7. Recent advancements in solid electrolytes integrated into all-solid-state 2D and 3D lithium-ion microbatteries vol.9, pp.27, 2017, https://doi.org/10.1039/d1ta02652f
  8. Crystal Structure and Preparation of Li7La3Zr2O12 (LLZO) Solid-State Electrolyte and Doping Impacts on the Conductivity: An Overview vol.2, pp.3, 2021, https://doi.org/10.3390/electrochem2030026
  9. Stabilizing the Cathode/Electrolyte Interface Using a Dry-Processed Lithium Titanate Coating for All-Solid-State Batteries vol.33, pp.17, 2017, https://doi.org/10.1021/acs.chemmater.1c01123
  10. Perovskite Na-ion conductors developed from analogous Li3xLa2/3−xTiO3 (LLTO): chemo-mechanical and defect engineering vol.9, pp.37, 2017, https://doi.org/10.1039/d1ta04252a
  11. Enhanced Al/Ta co-doped Li7La3Zr2O12 ceramic electrolytes with the reduced Ta doping level for solid-state lithium batteries vol.56, pp.35, 2017, https://doi.org/10.1007/s10853-021-06514-9