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Title: Effect of Liquid Electrolyte Soaking on the Interfacial Resistance of Li7La3Zr2O12 for All-Solid-State Lithium Batteries

Abstract

In this work, the impact of liquid electrolyte soaking on the interfacial resistance between the garnet-structured Li7La3Zr2O12 (LLZO) solid electrolyte and metallic lithium has been studied. Lithium carbonate (Li2CO3) formed by inadvertent exposure of LLZO to ambient conditions is generally known to increase interfacial impedance and decrease lithium wettability. Soaking LLZO powders and pellets in the electrolyte containing lithium tetrafluoroborate (LiBF4) shows a significantly reduced interfacial resistance and improved contact between lithium and LLZO. Raman spectroscopy, X-ray diffraction, and soft X-ray absorption spectroscopy reveal how Li2CO3 is continuously removed with increasing soaking time. On-line mass spectrometry and free energy calculations show how LiBF4 reacts with surface carbonate to form carbon dioxide. Using a very simple and scalable process that does not involve heat-treatment and expensive coating techniques, we show that the Li–LLZO interfacial resistance can be reduced by an order of magnitude.

Authors:
 [1];  [2]; ORCiD logo [3];  [3];  [4];  [5]; ORCiD logo [5];  [3]; ORCiD logo [6]; ORCiD logo [3]
+ Show Author Affiliations
  1. Robert Bosch LLC, Sunnyvale, CA (United States); Karlsruhe Inst. of Technology (KIT) (Germany)
  2. Robert Bosch LLC, Sunnyvale, CA (United States); Univ. of Strasbourg (France)
  3. Robert Bosch LLC, Sunnyvale, CA (United States)
  4. Holo, Inc., Oakland, CA (United States)
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1638158
Grant/Contract Number:  
AC02-76SF00515; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 12; Journal Issue: 18; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; LLZO; all-solid-state battery; lithium-ion battery; garnets; interfacial resistance

Citation Formats

Besli, Münir M., Usubelli, Camille, Metzger, Michael, Pande, Vikram, Harry, Katherine, Nordlund, Dennis, Sainio, Sami, Christensen, Jake, Doeff, Marca M., and Kuppan, Saravanan. Effect of Liquid Electrolyte Soaking on the Interfacial Resistance of Li7La3Zr2O12 for All-Solid-State Lithium Batteries. United States: N. p., 2020. Web. doi:10.1021/acsami.0c06194.
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Besli, Münir M., Usubelli, Camille, Metzger, Michael, Pande, Vikram, Harry, Katherine, Nordlund, Dennis, Sainio, Sami, Christensen, Jake, Doeff, Marca M., & Kuppan, Saravanan. Effect of Liquid Electrolyte Soaking on the Interfacial Resistance of Li7La3Zr2O12 for All-Solid-State Lithium Batteries. United States. https://doi.org/10.1021/acsami.0c06194
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Besli, Münir M., Usubelli, Camille, Metzger, Michael, Pande, Vikram, Harry, Katherine, Nordlund, Dennis, Sainio, Sami, Christensen, Jake, Doeff, Marca M., and Kuppan, Saravanan. Tue . "Effect of Liquid Electrolyte Soaking on the Interfacial Resistance of Li7La3Zr2O12 for All-Solid-State Lithium Batteries". United States. https://doi.org/10.1021/acsami.0c06194. https://www.osti.gov/servlets/purl/1638158.
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@article{osti_1638158,
title = {Effect of Liquid Electrolyte Soaking on the Interfacial Resistance of Li7La3Zr2O12 for All-Solid-State Lithium Batteries},
author = {Besli, Münir M. and Usubelli, Camille and Metzger, Michael and Pande, Vikram and Harry, Katherine and Nordlund, Dennis and Sainio, Sami and Christensen, Jake and Doeff, Marca M. and Kuppan, Saravanan},
abstractNote = {In this work, the impact of liquid electrolyte soaking on the interfacial resistance between the garnet-structured Li7La3Zr2O12 (LLZO) solid electrolyte and metallic lithium has been studied. Lithium carbonate (Li2CO3) formed by inadvertent exposure of LLZO to ambient conditions is generally known to increase interfacial impedance and decrease lithium wettability. Soaking LLZO powders and pellets in the electrolyte containing lithium tetrafluoroborate (LiBF4) shows a significantly reduced interfacial resistance and improved contact between lithium and LLZO. Raman spectroscopy, X-ray diffraction, and soft X-ray absorption spectroscopy reveal how Li2CO3 is continuously removed with increasing soaking time. On-line mass spectrometry and free energy calculations show how LiBF4 reacts with surface carbonate to form carbon dioxide. Using a very simple and scalable process that does not involve heat-treatment and expensive coating techniques, we show that the Li–LLZO interfacial resistance can be reduced by an order of magnitude.},
doi = {10.1021/acsami.0c06194},
journal = {ACS Applied Materials and Interfaces},
number = 18,
volume = 12,
place = {United States},
year = {Tue Apr 14 00:00:00 EDT 2020},
month = {Tue Apr 14 00:00:00 EDT 2020}
}
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https://doi.org/10.1021/acsami.0c06194
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