Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Kinetic versus Thermodynamic Stability of LLZO in Contact with Lithium Metal

Journal Article · · Chemistry of Materials
 [1];  [2];  [2];  [2];  [1];  [2];  [3];  [3];  [1];  [2]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Justus-Liebig-University Giessen, Giessen (Germany)
  3. Univ. of Michigan, Ann Arbor, MI (United States)
+ Show Author Affiliations
Li7La3Zr2O12 (LLZO) garnet-based oxides are a promising class of solid electrolytes used as the separator in all-solid-state batteries (ASSBs). While LLZO is considered to have a wide electrochemical stability window, its intrinsic stability in contact with lithium metal is not sufficiently well understood, and there is still a debate on the key question of whether LLZO does or does not form passivation layers before and during cycling. Utilizing both in situ and operando X-ray photoelectron spectroscopy techniques, in this work we reveal the presence of a kinetic barrier to the reduction of LLZO by Li metal, with the extent of oxygen-deficient interphase (ODI) formation depending sensitively on the energetics of Li metal arriving at the Li vertical bar LLZO interface. Despite the clear presence of a kinetic barrier to reduction, the electrochemical response of the Li vertical bar LLZO interface is unchanged by the presence of the ODI, indicating that ODI formation during electrochemical cycling does not hinder charge transfer across the Li vertical bar LLZO interface. Overall, these results reveal that the reactivity of LLZO with Li metal depends not only on the material properties of the adjoining phases (i.e., surface purity and active contact) and their resulting thermodynamic stability but also on the energy input at the interface and the resulting reaction kinetics. Furthermore, the presence of a kinetic barrier to reduction highlights the additional complexities governing the reactivity of solid-state interfaces in ASSBs and underscores the importance of operando characterization of interfacial stability to design more robust, high-performance protection strategies for solid electrolytes in contact with reactive electrodes.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
Funds of the Chemical Industry (FCI); German Federal Ministry of Education and Research (BMBF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1764985
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 23 Vol. 32; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (41)

Anode-Free Rechargeable Lithium Metal Batteries journal August 2016
Electroceramics: Characterization by Impedance Spectroscopy journal March 1990
Dopant‐Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal journal January 2019
Theoretical versus Practical Energy: A Plea for More Transparency in the Energy Calculation of Different Rechargeable Battery Systems journal June 2019
Fast Lithium Ion Conduction in Garnet-Type Li7La3Zr2O12 journal October 2007
Chemical stability of cubic Li7La3Zr2O12 with molten lithium at elevated temperature journal April 2013
The effect of roughness on the impedance of the interface between a solid electrolyte and a blocking electrode journal September 1976
Alkali Metal Anodes for Rechargeable Batteries journal February 2019
Superionic conduction and interfacial properties of the low temperature phase Li7P2S8Br0.5I0.5 journal May 2019
Unlocking the Energy Capabilities of Lithium Metal Electrode with Solid-State Electrolytes journal September 2018
Lithium-Metal Growth Kinetics on LLZO Garnet-Type Solid Electrolytes journal August 2019
Impedance characterization reveals mixed conducting interphases between sulfidic superionic conductors and lithium metal electrodes journal June 2017
Present understanding of the stability of Li-stuffed garnets with moisture, carbon dioxide, and metallic lithium journal June 2018
Interphase formation on lithium solid electrolytes—An in situ approach to study interfacial reactions by photoelectron spectroscopy journal October 2015
Interface Stability in Solid-State Batteries journal December 2015
Surface Chemistry Mechanism of Ultra-Low Interfacial Resistance in the Solid-State Electrolyte Li 7 La 3 Zr 2 O 12 journal September 2017
Physicochemical Concepts of the Lithium Metal Anode in Solid-State Batteries journal July 2020
Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review journal July 2017
Garnet-Type Solid-State Electrolytes: Materials, Interfaces, and Batteries journal April 2020
Interface Instability of Fe-Stabilized Li 7 La 3 Zr 2 O 12 versus Li Metal journal February 2018
Interfacial Stability of Li Metal–Solid Electrolyte Elucidated via in Situ Electron Microscopy journal October 2016
Solid-State Lithium–Sulfur Batteries Operated at 37 °C with Composites of Nanostructured Li 7 La 3 Zr 2 O 12 /Carbon Foam and Polymer journal April 2017
Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations journal October 2015
Crystal Orientation-Dependent Reactivity of Oxide Surfaces in Contact with Lithium Metal journal April 2018
Toward a Fundamental Understanding of the Lithium Metal Anode in Solid-State Batteries—An Electrochemo-Mechanical Study on the Garnet-Type Solid Electrolyte Li 6.25 Al 0.25 La 3 Zr 2 O 12 journal March 2019
Electrochemical Window of the Li-Ion Solid Electrolyte Li 7 La 3 Zr 2 O 12 journal January 2017
Computational Screening of Current Collectors for Enabling Anode-Free Lithium Metal Batteries journal October 2019
Issues and challenges facing rechargeable lithium batteries journal November 2001
A solid future for battery development journal September 2016
Reviving the lithium metal anode for high-energy batteries journal March 2017
Operando X-ray photoelectron spectroscopy of solid electrolyte interphase formation and evolution in Li2S-P2S5 solid-state electrolytes journal June 2018
Benchmarking the performance of all-solid-state lithium batteries journal March 2020
High-energy long-cycling all-solid-state lithium metal batteries enabled by silver–carbon composite anodes journal March 2020
Polymer electrolytes for lithium polymer batteries journal January 2016
Impact of air exposure and surface chemistry on Li–Li 7 La 3 Zr 2 O 12 interfacial resistance journal January 2017
Comparison of computational methods for the electrochemical stability window of solid-state electrolyte materials journal January 2020
The natural critical current density limit for Li 7 La 3 Zr 2 O 12 garnets journal January 2020
Garnet-type solid-state fast Li ion conductors for Li batteries: critical review journal January 2014
Transport Number Gradients and Solid Electrolyte Degradation journal January 1982
Compatibility of Li[sub 7]La[sub 3]Zr[sub 2]O[sub 12] Solid Electrolyte to All-Solid-State Battery Using Li Metal Anode journal January 2010
Comparison of computational methods for the electrochemical stability window of solid-state electrolyte materials dataset January 2019

Similar Records

Dopant-Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal
Journal Article · Sat Feb 09 19:00:00 EST 2019 · Advanced Energy Materials · OSTI ID:1508374
Elastic Properties of the Solid Electrolyte Li7La3Zr2O12 (LLZO)
Journal Article · Tue Dec 15 19:00:00 EST 2015 · Chemistry of Materials · OSTI ID:1261353

Related Subjects

25 ENERGY STORAGE
SEI formation
lithium metal anode
solid electrolyte
solid-state battery