Thermal Recovery of the Electrochemically Degraded LiCoO2/Li7La3Zr2O12:Al,Ta Interface in an All-Solid-State Lithium Battery

Martin Ihrig; Liang-Yin Kuo; Sandra Lobe; Alexander M Laptev; Che-An Lin; Chia-Hao Tu; Ruijie Ye; Payam Kaghazchi; Luca Cressa; Santhana Eswara; Shih-Kang Lin; Olivier Guillon; Dina Fattakhova-Rohlfing; Martin Finsterbusch

doi:10.1021/acsami.2c20004

Thermal Recovery of the Electrochemically Degraded LiCoO₂/Li₇La₃Zr₂O₁₂:Al,Ta Interface in an All-Solid-State Lithium Battery

ACS Appl Mater Interfaces. 2023 Jan 25;15(3):4101-4112. doi: 10.1021/acsami.2c20004. Epub 2023 Jan 16.

Authors

Martin Ihrig¹, Liang-Yin Kuo², Sandra Lobe¹, Alexander M Laptev³, Che-An Lin⁴, Chia-Hao Tu⁵, Ruijie Ye¹, Payam Kaghazchi^{1

6}, Luca Cressa⁷, Santhana Eswara⁷, Shih-Kang Lin^{4

5

8}, Olivier Guillon^{1

9}, Dina Fattakhova-Rohlfing^{1

10}, Martin Finsterbusch¹

Affiliations

¹ Institute of Energy and Climate Research - Materials Synthesis and Processing, Forschungszentrum Jülich GmbH, 52425Jülich, Germany.
² Department of Chemical Engineering, Ming Chi University of Technology, No. 84, Gungjuan Road, New Taipei City24301, Taiwan.
³ Łukasiewicz Research Network - Poznan Institute of Technology, 6 Ewarysta Estkowskiego St., 61-755Poznań, Poland.
⁴ Department of Materials Science and Engineering, National Cheng Kung University, No. 1, University Road, Tainan City701, Taiwan.
⁵ Hierarchical Green-Energy Materials Research Center, National Cheng Kung University, No. 1, University Road, Tainan City701, Taiwan.
⁶ MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, Enschede7500AE, The Netherlands.
⁷ Luxembourg Institute of Science and Technology, Advanced Instrumentation for Nano-Analytics (AINA), rue du Brill 41, 4422Belvaux, Luxembourg.
⁸ Program on Smart and Sustainable Manufacturing, Academy of Innovative Semiconductor and Sustainable Manufacturing, National Cheng Kung University, Tainan City701, Taiwan.
⁹ Jülich-Aachen Research Alliance: JARA-ENERGY, 52425Jülich, Germany.
¹⁰ Faculty of Engineering and Center for Nanointegration Duisburg-Essen, University Duisburg-Essen, Lotharstr. 1, 47057Duisburg, Germany.

Abstract

All-solid-state lithium batteries are promising candidates for next-generation energy storage systems. Their performance critically depends on the capacity and cycling stability of the cathodic layer. Cells with a garnet Li₇La₃Zr₂O₁₂ (LLZO) electrolyte can show high areal storage capacity. However, they commonly suffer from performance degradation during cycling. For fully inorganic cells based on LiCoO₂ (LCO) as cathode active material and LLZO, the electrochemically induced interface amorphization has been identified as an origin of the performance degradation. This study shows that the amorphized interface can be recrystallized by thermal recovery (annealing) with nearly full restoration of the cell performance. The structural and chemical changes at the LCO/LLZO heterointerface associated with degradation and recovery were analyzed in detail and justified by thermodynamic modeling. Based on this comprehensive understanding, this work demonstrates a facile way to recover more than 80% of the initial storage capacity through a thermal recovery (annealing) step. The thermal recovery can be potentially used for cost-efficient recycling of ceramic all-solid-state batteries.

Keywords: ASSLB; cathode/garnet interface; interface degradation; interface recovery; solid-state Li battery; thermal treatment.