Garnet Electrolyte Surface Degradation and Recovery

Cheng, Lei; Liu, Miao; Mehta, Apurva; Xin, Huolin; Lin, Feng; Persson, Kristin; Chen, Guoying; Crumlin, Ethan J.; Doeff, Marca

doi:10.1021/acsaem.8b01723

Title: Garnet Electrolyte Surface Degradation and Recovery

Journal Article · 30 November 2018 · ACS Applied Energy Materials

DOI: https://doi.org/10.1021/acsaem.8b01723 · OSTI ID:1630607

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Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

Ceramic materials based on the garnet structure Li₇La₃Zr₂O₁₂ (LLZO) show great promise as lithium-ion conducting electrolytes for solid-state lithium batteries. However, these materials exhibit surface degradation when exposed to air and moisture, which adversely impacts their functioning in operating devices. In this work, we use several depth-profiling and in situ techniques to probe the nature of the surface reactions that occur when aluminum (Al)-substituted LLZO is exposed to air. These experiments show that a proton exchange reaction occurs near the surface of the LLZO and leads to change in its chemistry and structure, concomitant with the formation of Li₂CO₃. But these reactions can be readily reversed by heating samples at 250 °C under an inert atmosphere to recover LLZO surface chemistry and structure. Symmetrical cells containing samples treated this way exhibited much lower area specific impedances than those containing air-exposed LLZO without the treatment, confirming the reversal of the degradation process. Finally, our results show a process to rejuvenate LLZO surface, and this opens the possibility of integrating this material in solid-state devices.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515; SC0012704

OSTI ID:: 1630607

Journal Information:: ACS Applied Energy Materials, Vol. 1, Issue 12; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 72 works

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References (44)

Challenges for Rechargeable Li Batteries Goodenough, John B.; Kim, Youngsik Chemistry of Materials, Vol. 22, Issue 3, p. 587-603 https://doi.org/10.1021/cm901452z	journal	February 2010
A solid future for battery development Janek, Jürgen; Zeier, Wolfgang G. Nature Energy, Vol. 1, Issue 9 https://doi.org/10.1038/nenergy.2016.141	journal	September 2016
New horizons for inorganic solid state ion conductors Zhang, Zhizhen; Shao, Yuanjun; Lotsch, Bettina Energy & Environmental Science, Vol. 11, Issue 8 https://doi.org/10.1039/C8EE01053F	journal	January 2018
Interface Stability in Solid-State Batteries Richards, William D.; Miara, Lincoln J.; Wang, Yan Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b04082	journal	December 2015
Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations Zhu, Yizhou; He, Xingfeng; Mo, Yifei ACS Applied Materials & Interfaces, Vol. 7, Issue 42 https://doi.org/10.1021/acsami.5b07517	journal	October 2015
First principles study on electrochemical and chemical stability of solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries Zhu, Yizhou; He, Xingfeng; Mo, Yifei Journal of Materials Chemistry A, Vol. 4, Issue 9 https://doi.org/10.1039/C5TA08574H	journal	January 2016
Synchrotron X-ray Analytical Techniques for Studying Materials Electrochemistry in Rechargeable Batteries Lin, Feng; Liu, Yijin; Yu, Xiqian Chemical Reviews, Vol. 117, Issue 21 https://doi.org/10.1021/acs.chemrev.7b00007	journal	September 2017
Degradation of NASICON-Type Materials in Contact with Lithium Metal: Formation of Mixed Conducting Interphases (MCI) on Solid Electrolytes Hartmann, Pascal; Leichtweiss, Thomas; Busche, Martin R. The Journal of Physical Chemistry C, Vol. 117, Issue 41 https://doi.org/10.1021/jp4051275	journal	October 2013
Local structure and composition change at surface of lithium-ion conducting solid electrolyte Yamada, Hirotoshi; Takemoto, Koshin Solid State Ionics, Vol. 285 https://doi.org/10.1016/j.ssi.2015.08.019	journal	February 2016
Fast Lithium Ion Conduction in Garnet-Type Li₇La₃Zr₂O₁₂ Murugan, Ramaswamy; Thangadurai, Venkataraman; Weppner, Werner Angewandte Chemie International Edition, Vol. 46, Issue 41, p. 7778-7781 https://doi.org/10.1002/anie.200701144	journal	October 2007
Fast Solid-State Li Ion Conducting Garnet-Type Structure Metal Oxides for Energy Storage Thangadurai, Venkataraman; Pinzaru, Dana; Narayanan, Sumaletha The Journal of Physical Chemistry Letters, Vol. 6, Issue 2 https://doi.org/10.1021/jz501828v	journal	January 2015
Garnet-type solid-state fast Li ion conductors for Li batteries: critical review Thangadurai, Venkataraman; Narayanan, Sumaletha; Pinzaru, Dana Chemical Society Reviews, Vol. 43, Issue 13 https://doi.org/10.1039/c4cs00020j	journal	January 2014
The origin of high electrolyte–electrode interfacial resistances in lithium cells containing garnet type solid electrolytes Cheng, Lei; Crumlin, Ethan J.; Chen, Wei Phys. Chem. Chem. Phys., Vol. 16, Issue 34 https://doi.org/10.1039/C4CP02921F	journal	January 2014
Effect of microstructure and surface impurity segregation on the electrical and electrochemical properties of dense Al-substituted Li ₇ La ₃ Zr ₂ O ₁₂ Cheng, Lei; Park, Joong Sun; Hou, Huaming J. Mater. Chem. A, Vol. 2, Issue 1 https://doi.org/10.1039/C3TA13999A	journal	January 2014
Influence of Li ⁺ and H ⁺ Distribution on the Crystal Structure of Li _{7– x} H _x La ₃ Zr ₂ O ₁₂ (0 ≤ x ≤ 5) Garnets Orera, Alodia; Larraz, Guillermo; Rodríguez-Velamazán, José Alberto Inorganic Chemistry, Vol. 55, Issue 3 https://doi.org/10.1021/acs.inorgchem.5b02708	journal	January 2016
Cubic phases of garnet-type Li7La3Zr2O12: the role of hydration Larraz, G.; Orera, A.; Sanjuán, M. L. Journal of Materials Chemistry A, Vol. 1, Issue 37 https://doi.org/10.1039/c3ta11996c	journal	January 2013
Surface Chemistry Mechanism of Ultra-Low Interfacial Resistance in the Solid-State Electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ Sharafi, Asma; Kazyak, Eric; Davis, Andrew L. Chemistry of Materials, Vol. 29, Issue 18 https://doi.org/10.1021/acs.chemmater.7b03002	journal	September 2017
Impact of air exposure and surface chemistry on Li–Li ₇ La ₃ Zr ₂ O ₁₂ interfacial resistance Sharafi, Asma; Yu, Seungho; Naguib, Michael Journal of Materials Chemistry A, Vol. 5, Issue 26 https://doi.org/10.1039/C7TA03162A	journal	January 2017
Interrelationships among Grain Size, Surface Composition, Air Stability, and Interfacial Resistance of Al-Substituted Li ₇ La ₃ Zr ₂ O ₁₂ Solid Electrolytes Cheng, Lei; Wu, Cheng Hao; Jarry, Angelique ACS Applied Materials & Interfaces, Vol. 7, Issue 32 https://doi.org/10.1021/acsami.5b02528	journal	August 2015
Stability of garnet-type Li ion conductors: An overview Duan, Huanan; Zheng, Hongpeng; Zhou, Ying Solid State Ionics, Vol. 318 https://doi.org/10.1016/j.ssi.2017.09.018	journal	May 2018
Ionic Conductivity and Air Stability of Al-Doped Li ₇ La ₃ Zr ₂ O ₁₂ Sintered in Alumina and Pt Crucibles Xia, Wenhao; Xu, Biyi; Duan, Huanan ACS Applied Materials & Interfaces, Vol. 8, Issue 8 https://doi.org/10.1021/acsami.5b12186	journal	February 2016
Garnet Electrolytes for Solid State Batteries: Visualization of Moisture-Induced Chemical Degradation and Revealing Its Impact on the Li-Ion Dynamics Brugge, Rowena H.; Hekselman, A. K. Ola; Cavallaro, Andrea Chemistry of Materials, Vol. 30, Issue 11 https://doi.org/10.1021/acs.chemmater.8b00486	journal	May 2018
Present understanding of the stability of Li-stuffed garnets with moisture, carbon dioxide, and metallic lithium Hofstetter, Kyle; Samson, Alfred Junio; Narayanan, Sumaletha Journal of Power Sources, Vol. 390 https://doi.org/10.1016/j.jpowsour.2018.04.016	journal	June 2018
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
New ambient pressure photoemission endstation at Advanced Light Source beamline 9.3.2 Grass, Michael E.; Karlsson, Patrik G.; Aksoy, Funda Review of Scientific Instruments, Vol. 81, Issue 5 https://doi.org/10.1063/1.3427218	journal	May 2010
Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis Ong, Shyue Ping; Richards, William Davidson; Jain, Anubhav Computational Materials Science, Vol. 68 https://doi.org/10.1016/j.commatsci.2012.10.028	journal	February 2013
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
A high-throughput infrastructure for density functional theory calculations Jain, Anubhav; Hautier, Geoffroy; Moore, Charles J. Computational Materials Science, Vol. 50, Issue 8 https://doi.org/10.1016/j.commatsci.2011.02.023	journal	June 2011
Crystal Chemistry and Stability of “Li₇La₃Zr₂O₁₂ ” Garnet: A Fast Lithium-Ion Conductor Geiger, Charles A.; Alekseev, Evgeny; Lazic, Biljana Inorganic Chemistry, Vol. 50, Issue 3, p. 1089-1097 https://doi.org/10.1021/ic101914e	journal	February 2011
Full correction of the self-absorption in soft-fluorescence extended x-ray-absorption fine structure Tröger, L.; Arvanitis, D.; Baberschke, K. Physical Review B, Vol. 46, Issue 6 https://doi.org/10.1103/PhysRevB.46.3283	journal	August 1992
First Total H ⁺ /Li ⁺ Ion Exchange in Garnet-Type Li ₅ La ₃ Nb ₂ O ₁₂ Using Organic Acids and Studies on the Effect of Li Stuffing Truong, Lina; Thangadurai, Venkataraman Inorganic Chemistry, Vol. 51, Issue 3 https://doi.org/10.1021/ic202491m	journal	January 2012
NMR study of Li distribution in Li _7−x H _x La ₃ Zr ₂ O ₁₂ garnets Larraz, G.; Orera, A.; Sanz, J. Journal of Materials Chemistry A, Vol. 3, Issue 10 https://doi.org/10.1039/C4TA04570J	journal	January 2015
Effects of Li source on microstructure and ionic conductivity of Al-contained Li6.75La3Zr1.75Ta0.25O12 ceramics Ren, Yaoyu; Deng, Hui; Chen, Rujun Journal of the European Ceramic Society, Vol. 35, Issue 2 https://doi.org/10.1016/j.jeurceramsoc.2014.09.007	journal	February 2015
High-temperature decomposition of lithium carbonate at atmospheric pressure Timoshevskii, A. N.; Ktalkherman, M. G.; Emel’kin, V. A. High Temperature, Vol. 46, Issue 3 https://doi.org/10.1134/S0018151X0803019X	journal	May 2008
Crystal Structure of Garnet-Related Li-Ion Conductor Li _{7–3 x} Ga _x La ₃ Zr ₂ O ₁₂ : Fast Li-Ion Conduction Caused by a Different Cubic Modification? Wagner, Reinhard; Redhammer, Günther J.; Rettenwander, Daniel Chemistry of Materials, Vol. 28, Issue 6 https://doi.org/10.1021/acs.chemmater.6b00038	journal	February 2016
Interface Instability of Fe-Stabilized Li ₇ La ₃ Zr ₂ O ₁₂ versus Li Metal Rettenwander, Daniel; Wagner, Reinhard; Reyer, Andreas The Journal of Physical Chemistry C, Vol. 122, Issue 7 https://doi.org/10.1021/acs.jpcc.7b12387	journal	February 2018
Fast Li-Ion-Conducting Garnet-Related Li _{7–3 x} Fe _x La ₃ Zr ₂ O ₁₂ with Uncommon I 4̅3 d Structure Wagner, Reinhard; Redhammer, Günther J.; Rettenwander, Daniel Chemistry of Materials, Vol. 28, Issue 16 https://doi.org/10.1021/acs.chemmater.6b02516	journal	August 2016
Structural and Electrochemical Consequences of Al and Ga Cosubstitution in Li ₇ La ₃ Zr ₂ O ₁₂ Solid Electrolytes Rettenwander, Daniel; Redhammer, Günther; Preishuber-Pflügl, Florian Chemistry of Materials, Vol. 28, Issue 7 https://doi.org/10.1021/acs.chemmater.6b00579	journal	March 2016
Effect of Li+/H+ exchange in water treated Ta-doped Li7La3Zr2O12 Yow, Zhen Feng; Oh, Yuan Liang; Gu, Wenyi Solid State Ionics, Vol. 292 https://doi.org/10.1016/j.ssi.2016.05.016	journal	September 2016
Instability of the Lithium Garnet Li ₇ La ₃ Sn ₂ O ₁₂ : Li ⁺ /H ⁺ Exchange and Structural Study Galven, Cyrille; Fourquet, Jean-Louis; Crosnier-Lopez, Marie-Pierre Chemistry of Materials, Vol. 23, Issue 7 https://doi.org/10.1021/cm103595x	journal	April 2011
Effect of Surface Microstructure on Electrochemical Performance of Garnet Solid Electrolytes Cheng, Lei; Chen, Wei; Kunz, Martin ACS Applied Materials & Interfaces, Vol. 7, Issue 3 https://doi.org/10.1021/am508111r	journal	January 2015
Enhanced lithium ion transport in garnet-type solid state electrolytes Cheng, Lei; Hou, Huaming; Lux, Simon Journal of Electroceramics, Vol. 38, Issue 2-4 https://doi.org/10.1007/s10832-017-0080-3	journal	March 2017