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Title: Atomic Layer Deposition of the Solid Electrolyte Garnet Li 7 La 3 Zr 2 O 12

Abstract

Lithium solid electrolytes are a promising platform for achieving high energy density, long-lasting, and safe rechargeable batteries, which could have widespread societal impact. In particular, the ceramic oxide garnet Li7La3Zr2O12 (LLZO) has been shown to be a promising electrolyte due to its stability and high ionic conductivity. Two major challenges for commercialization are manufacturing of thin layers and creating stable, low-impedance, interfaces with both anode and cathode materials. Atomic Layer Deposition (ALD) has recently been shown as a potential method for depositing both solid electrolytes and interfacial layers to improve the stability and performance at electrode-electrolyte interfaces in battery systems. Herein we present the first reported ALD process for LLZO, demonstrating the ability to tune composition within the amorphous film and anneal to achieve the desired cubic garnet phase. Formation of the cubic phase was observed at temperatures as low as 555°C, significantly lower than is required for bulk processing. Additionally, challenges associated with achieving a dense garnet phase due to substrate reactivity, morphology changes and Li loss under the necessary high temperature annealing are quantified via in situ synchrotron diffraction.

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [1];  [1];  [1];  [2]; ORCiD logo [3];  [1]; ORCiD logo [1]
  1. Department of Mechanical Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States
  2. Department of Mechanical Engineering and Materials Science, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States
  3. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE Advanced Research Projects Agency - Energy (ARPA-E)
OSTI Identifier:
1390428
Report Number(s):
PNNL-SA-124464
Journal ID: ISSN 0897-4756; 48885; KP1704020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry of Materials; Journal Volume: 29; Journal Issue: 8
Country of Publication:
United States
Language:
English
Subject:
solid electrolyte; Atomic layer deposition; LLZO; garnet; Environmental Molecular Sciences Laboratory

Citation Formats

Kazyak, Eric, Chen, Kuan-Hung, Wood, Kevin N., Davis, Andrew L., Thompson, Travis, Bielinski, Ashley R., Sanchez, Adrian J., Wang, Xiang, Wang, Chongmin, Sakamoto, Jeff, and Dasgupta, Neil P.. Atomic Layer Deposition of the Solid Electrolyte Garnet Li 7 La 3 Zr 2 O 12. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b00944.
Kazyak, Eric, Chen, Kuan-Hung, Wood, Kevin N., Davis, Andrew L., Thompson, Travis, Bielinski, Ashley R., Sanchez, Adrian J., Wang, Xiang, Wang, Chongmin, Sakamoto, Jeff, & Dasgupta, Neil P.. Atomic Layer Deposition of the Solid Electrolyte Garnet Li 7 La 3 Zr 2 O 12. United States. doi:10.1021/acs.chemmater.7b00944.
Kazyak, Eric, Chen, Kuan-Hung, Wood, Kevin N., Davis, Andrew L., Thompson, Travis, Bielinski, Ashley R., Sanchez, Adrian J., Wang, Xiang, Wang, Chongmin, Sakamoto, Jeff, and Dasgupta, Neil P.. Thu . "Atomic Layer Deposition of the Solid Electrolyte Garnet Li 7 La 3 Zr 2 O 12". United States. doi:10.1021/acs.chemmater.7b00944.
@article{osti_1390428,
title = {Atomic Layer Deposition of the Solid Electrolyte Garnet Li 7 La 3 Zr 2 O 12},
author = {Kazyak, Eric and Chen, Kuan-Hung and Wood, Kevin N. and Davis, Andrew L. and Thompson, Travis and Bielinski, Ashley R. and Sanchez, Adrian J. and Wang, Xiang and Wang, Chongmin and Sakamoto, Jeff and Dasgupta, Neil P.},
abstractNote = {Lithium solid electrolytes are a promising platform for achieving high energy density, long-lasting, and safe rechargeable batteries, which could have widespread societal impact. In particular, the ceramic oxide garnet Li7La3Zr2O12 (LLZO) has been shown to be a promising electrolyte due to its stability and high ionic conductivity. Two major challenges for commercialization are manufacturing of thin layers and creating stable, low-impedance, interfaces with both anode and cathode materials. Atomic Layer Deposition (ALD) has recently been shown as a potential method for depositing both solid electrolytes and interfacial layers to improve the stability and performance at electrode-electrolyte interfaces in battery systems. Herein we present the first reported ALD process for LLZO, demonstrating the ability to tune composition within the amorphous film and anneal to achieve the desired cubic garnet phase. Formation of the cubic phase was observed at temperatures as low as 555°C, significantly lower than is required for bulk processing. Additionally, challenges associated with achieving a dense garnet phase due to substrate reactivity, morphology changes and Li loss under the necessary high temperature annealing are quantified via in situ synchrotron diffraction.},
doi = {10.1021/acs.chemmater.7b00944},
journal = {Chemistry of Materials},
number = 8,
volume = 29,
place = {United States},
year = {Thu Apr 13 00:00:00 EDT 2017},
month = {Thu Apr 13 00:00:00 EDT 2017}
}
  • The thermal expansion (TE) coefficients of the lithium-stable lithium-ion conducting garnet lithium lanthanum zirconium oxide (LLZ) and the effect of aluminum substitution were measured from room temperature up to 700 °C by a synchrotron-based X-ray diffraction. The typical TE value measured for the most reported composition (LLZ doped with 0.3 wt.% or 0.093 mol% aluminum) was 15.498 × 10-6 K-1, which is approximately twice the value reported for other garnet-type structures. As the Al(III) concentration has been observed to strongly affect the structure observed and the ionic conductivity, we also assessed its role on thermal expansion and noted only amore » small variation with increasing dopant concentration. The materials implications for using LLZ in a solid state battery are discussed.« less
  • The electrochemical stability window of solid electrolyte is overestimated by the conventional experimental method using a Li/electrolyte/inert metal semiblocking electrode because of the limited contact area between solid electrolyte and inert metal. Since the battery is cycled in the overestimated stability window, the decomposition of the solid electrolyte at the interfaces occurs but has been ignored as a cause for high interfacial resistances in previous studies, limiting the performance improvement of the bulk-type solid-state battery despite the decades of research efforts. Thus, there is an urgent need to identify the intrinsic stability window of the solid electrolyte. The thermodynamic electrochemicalmore » stability window of solid electrolytes is calculated using first principles computation methods, and an experimental method is developed to measure the intrinsic electrochemical stability window of solid electrolytes using a Li/electrolyte/electrolyte-carbon cell. The most promising solid electrolytes, Li10GeP2S12 and cubic Li-garnet Li7La3Zr2O12, are chosen as the model materials for sulfide and oxide solid electrolytes, respectively. The results provide valuable insights to address the most challenging problems of the interfacial stability and resistance in high-performance solid-state batteries.« less
  • The electrochemical stability window of solid electrolyte is overestimated by the conventional experimental method using a Li/electrolyte/inert metal semiblocking electrode because of the limited contact area between solid electrolyte and inert metal. Since the battery is cycled in the overestimated stability window, the decomposition of the solid electrolyte at the interfaces occurs but has been ignored as a cause for high interfacial resistances in previous studies, limiting the performance improvement of the bulk-type solid-state battery despite the decades of research efforts. Thus, there is an urgent need to identify the intrinsic stability window of the solid electrolyte. The thermodynamic electrochemicalmore » stability window of solid electrolytes is calculated using first principles computation methods, and an experimental method is developed to measure the intrinsic electrochemical stability window of solid electrolytes using a Li/electrolyte/electrolyte-carbon cell. The most promising solid electrolytes, Li10GeP2S12 and cubic Li-garnet Li7La3Zr2O12, are chosen as the model materials for sulfide and oxide solid electrolytes, respectively. The results provide valuable insights to address the most challenging problems of the interfacial stability and resistance in high-performance solid-state batteries.« less