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Title: Bi aliovalent substitution in Li7La3Zr2O12 garnets: Structural and ionic conductivity effects

Abstract

We report on the synthesis of cubic-phase garnet-type solid-state electrolytes based on Bi-doped Li7La3Zr2O12 (LLZO). Bi aliovalent substitution of Zr in LLZO utilizing the Pechini processing method is employed to synthesize Li7-xLa3Zr2-xBixO12 compounds. A strong dependence of the ionic conductivity on Bi content is observed, and under our synthesis and sintering conditions, a >100-fold increase over the un-doped sample is observed for x=0.75. Cubic-phase Li6La3Zr1BiO12 compounds are generated upon annealing in air in the temperature range 650 °C-900 °C. In contrast, in the absence of Bi, the cubic garnet phase of Li7La3Zr2O12 is not formed below 700 °C and a transformation to the tetragonal phase is observed at similar to 900 °C for this un-doped compound. The role of Bi in lowering the formation temperature of the garnet cubic phase and in the ionic conductivity improvements is investigated in this work. We ascribe the effect of Bi-doping on ionic conductivity increments to changes in Li+-site occupancy and lattice parameters and the reduction in the formation temperature for the cubic-phase formation to rate enhancements of the solid-state reaction. To identify the site occupancy of Bi in the garnet structure, we employ synchrotron extended x-ray absorption fine structure spectroscopy. Our results indicatemore » that Bi additions occupy the Zr-type sites exclusively, to within the accuracy of the measurements.« less

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Purdue Univ., West Lafayette, IN (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Joint Center for Energy Storage Research (JCESR)
OSTI Identifier:
1647159
Alternate Identifier(s):
OSTI ID: 1602333
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
AIP Advances
Additional Journal Information:
Journal Volume: 10; Journal Issue: 3; Journal ID: ISSN 2158-3226
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Sintering; crystalline properties; ceramic materials; synchrotrons; ionic conductivity; scanning electron microscopy; X-ray absorption spectroscopy; solgels; electrolytes; batteries

Citation Formats

Schwanz, Derek K., Villa, Andres, Balasubramanian, Mahalingam, Helfrecht, Benjamin A., and Marinero, Ernesto E.. Bi aliovalent substitution in Li7La3Zr2O12 garnets: Structural and ionic conductivity effects. United States: N. p., 2020. Web. https://doi.org/10.1063/1.5141764.
Schwanz, Derek K., Villa, Andres, Balasubramanian, Mahalingam, Helfrecht, Benjamin A., & Marinero, Ernesto E.. Bi aliovalent substitution in Li7La3Zr2O12 garnets: Structural and ionic conductivity effects. United States. https://doi.org/10.1063/1.5141764
Schwanz, Derek K., Villa, Andres, Balasubramanian, Mahalingam, Helfrecht, Benjamin A., and Marinero, Ernesto E.. Mon . "Bi aliovalent substitution in Li7La3Zr2O12 garnets: Structural and ionic conductivity effects". United States. https://doi.org/10.1063/1.5141764. https://www.osti.gov/servlets/purl/1647159.
@article{osti_1647159,
title = {Bi aliovalent substitution in Li7La3Zr2O12 garnets: Structural and ionic conductivity effects},
author = {Schwanz, Derek K. and Villa, Andres and Balasubramanian, Mahalingam and Helfrecht, Benjamin A. and Marinero, Ernesto E.},
abstractNote = {We report on the synthesis of cubic-phase garnet-type solid-state electrolytes based on Bi-doped Li7La3Zr2O12 (LLZO). Bi aliovalent substitution of Zr in LLZO utilizing the Pechini processing method is employed to synthesize Li7-xLa3Zr2-xBixO12 compounds. A strong dependence of the ionic conductivity on Bi content is observed, and under our synthesis and sintering conditions, a >100-fold increase over the un-doped sample is observed for x=0.75. Cubic-phase Li6La3Zr1BiO12 compounds are generated upon annealing in air in the temperature range 650 °C-900 °C. In contrast, in the absence of Bi, the cubic garnet phase of Li7La3Zr2O12 is not formed below 700 °C and a transformation to the tetragonal phase is observed at similar to 900 °C for this un-doped compound. The role of Bi in lowering the formation temperature of the garnet cubic phase and in the ionic conductivity improvements is investigated in this work. We ascribe the effect of Bi-doping on ionic conductivity increments to changes in Li+-site occupancy and lattice parameters and the reduction in the formation temperature for the cubic-phase formation to rate enhancements of the solid-state reaction. To identify the site occupancy of Bi in the garnet structure, we employ synchrotron extended x-ray absorption fine structure spectroscopy. Our results indicate that Bi additions occupy the Zr-type sites exclusively, to within the accuracy of the measurements.},
doi = {10.1063/1.5141764},
journal = {AIP Advances},
number = 3,
volume = 10,
place = {United States},
year = {2020},
month = {3}
}

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