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Advanced Analytical Characterization of Interface Degradation in Ni-Rich NCM Cathode Co-Sintered with LATP Solid Electrolyte

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    Advanced Analytical Characterization of Interface Degradation in Ni-Rich NCM Cathode Co-Sintered with LATP Solid Electrolyte
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    • Michael Malaki
      Michael Malaki
      Materials Sciences Center (WZMW) and Department of Physics, Philipps University Marburg, Hans Meerwein Strasse 6, 35032 Marburg, Germany
      More by Michael Malaki
      Orcidhttps://orcid.org/0000-0001-7921-982X
    • Anuj Pokle
      Anuj Pokle
      Materials Sciences Center (WZMW) and Department of Physics, Philipps University Marburg, Hans Meerwein Strasse 6, 35032 Marburg, Germany
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    • Svenja-Katharina Otto
      Svenja-Katharina Otto
      Institute of Physical Chemistry and Center for Materials Research, Justus Liebig University Giessen, Heinrich-Buff-Ring 17, 35392 Giessen, Germany
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    • Anja Henss
      Anja Henss
      Institute of Physical Chemistry and Center for Materials Research, Justus Liebig University Giessen, Heinrich-Buff-Ring 17, 35392 Giessen, Germany
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      Orcidhttps://orcid.org/0000-0001-5009-6512
    • Jean Philippe Beaupain
      Jean Philippe Beaupain
      Fraunhofer Institute for Ceramic Technologies and Systems IKTS, Winterbergstrasse 28, 01277 Dresden, Germany
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      Orcidhttps://orcid.org/0000-0003-3320-6497
    • Andreas Beyer
      Andreas Beyer
      Materials Sciences Center (WZMW) and Department of Physics, Philipps University Marburg, Hans Meerwein Strasse 6, 35032 Marburg, Germany
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      Orcidhttps://orcid.org/0000-0001-6533-0631
    • Julian Müller
      Julian Müller
      Micro- and Nanoanalytics Group, University of Siegen, Paul-Bonatz Str. 9-11, 57076 Siegen, Germany
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    • Benjamin Butz
      Benjamin Butz
      Micro- and Nanoanalytics Group, University of Siegen, Paul-Bonatz Str. 9-11, 57076 Siegen, Germany
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    • Katja Wätzig
      Katja Wätzig
      Fraunhofer Institute for Ceramic Technologies and Systems IKTS, Winterbergstrasse 28, 01277 Dresden, Germany
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    • Mihails Kusnezoff
      Mihails Kusnezoff
      Fraunhofer Institute for Ceramic Technologies and Systems IKTS, Winterbergstrasse 28, 01277 Dresden, Germany
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    • Jürgen Janek
      Jürgen Janek
      Institute of Physical Chemistry and Center for Materials Research, Justus Liebig University Giessen, Heinrich-Buff-Ring 17, 35392 Giessen, Germany
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    • Kerstin Volz*
      Kerstin Volz
      Materials Sciences Center (WZMW) and Department of Physics, Philipps University Marburg, Hans Meerwein Strasse 6, 35032 Marburg, Germany
      *Email: [email protected]
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    ACS Applied Energy Materials

    Cite this: ACS Appl. Energy Mater. 2022, 5, 4, 4651–4663
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    https://doi.org/10.1021/acsaem.2c00084
    Published April 11, 2022
    Copyright © 2022 The Authors. Published by American Chemical Society
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    Abstract

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    Li-ion all-solid-state batteries (ASSBs) employing solid electrolytes (SEs) can address the energy density and safety issues that plague the current state-of-the-art Li-ion battery (LIB) architecture. To that end, intimate physical and chemical bonding has to be established between high-performance cathodes and high-voltage stable SEs to facilitate high Li+ transfer. The production of intimate interfaces in oxide cathode–solid electrolyte composites requires high-temperature (>1000 °C) processing, which results in a range of degradation products. Here, we report the morphological, structural, and chemical changes that occur in commercial Ni-rich layered LiNi0.6Co0.2Mn0.2O2 (NCM622) cathode in contact with oxide SE Li1.3Al0.3Ti1.7(PO4)3 (LATP) when cosintered between 550 °C and 650 °C. The structural evolution of pristine NCM622 heat-treated at a temperature of 650 °C is contrasted with the NCM622 from the composites using aberration-corrected scanning transmission electron microscopy (AC-STEM). At high spatial resolutions, the degradation of NCM particles in the composites proceeds via phase transitions from R3̅m (layered) to Fd3̅m (spinel) to Fm3̅m (rocksalt) to amorphous at the grain boundaries and via pit formations and intragranular crack nucleation and propagation in the bulk. Automated crystal orientation mapping (ACOM) in combination with low-dose TEM was used to investigate the beam-sensitive cathode–solid electrolyte interfaces. To provide statistical relevance to the investigations undertaken, ACOM-TEM was used in combination with time-of-flight secondary ion mass spectroscopy (ToF-SIMS). By combining these techniques, we show that the phase transitions of the NCM particles are correlated with simultaneous lithium transfer from NCM regions to LATP regions with evolving temperature.

    Copyright © 2022 The Authors. Published by American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsaem.2c00084.

    • STEM micrographs showing lamellae of all samples, NCM morphology and microstructure in the composites, models for different phases and zone-axis, STEM-EDX analysis of pristine reference materials and HR-STEM micrographs highlighting dislocations from pristine NCM material (PDF)

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    Cited By

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    This article is cited by 14 publications.

    1. Yunlong Duan, Shi-Peng Chen, Linnan Zhang, Liying Guo, Fa-Nian Shi. Review on Oxygen Release Mechanism and Modification Strategy of Nickel-Rich NCM Cathode Materials for Lithium-Ion Batteries: Recent Advances and Future Directions. Energy & Fuels 2024, 38 (7) , 5607-5631. https://doi.org/10.1021/acs.energyfuels.3c04636
    2. Zizheng Tong, Yan-Ming Lai, Chia-Erh Liu, Shih-Chieh Liao, Jin-Ming Chen, Shu-Fen Hu, Ru-Shi Liu. Degradation of a Li1.5Al0.5Ge1.5(PO4)3-Based Solid-State Li-Metal Battery: Corrosion of Li1.5Al0.5Ge1.5(PO4)3 against the Li-Metal Anode. ACS Applied Energy Materials 2022, 5 (9) , 11694-11704. https://doi.org/10.1021/acsaem.2c02170
    3. Timothée Fabre, Marie Lachal, Hari Raj, Valérie Pralong, Renaud Bouchet, Marlu César Steil. Li3V2(PO4)3 sintering atmosphere optimisation for its integration in all-solid-state batteries. Journal of the European Ceramic Society 2025, 45 (2) , 116941. https://doi.org/10.1016/j.jeurceramsoc.2024.116941
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    5. Ziye Wang, Yingshuai Wang, Yuhang Xin, Qingbo Zhou, Xiangyu Ding, Lei Liu, Tinglu Song, Feng Wu, Zhongbao Wei, Hongcai Gao. Simultaneous modulation of cathode/anode and electrolyte interfaces via a nitrile additive for high-energy-density lithium-metal batteries. Chemical Science 2024, 15 (40) , 16669-16680. https://doi.org/10.1039/D4SC04122D
    6. Likun Chen, Peiran Shi, Tian Gu, Jinshuo Mi, Ke Yang, Liang Zhao, Jianshuai Lv, Ming Liu, Yan-Bing He, Feiyu Kang. Strategies of constructing highly stable interfaces with low resistance in inorganic oxide-based solid-state lithium batteries. eScience 2024, 1 , 100277. https://doi.org/10.1016/j.esci.2024.100277
    7. Thomas Demuth, Till Fuchs, Andreas Beyer, Jürgen Janek, Kerstin Volz. “Depo-all-around”: A novel FIB-based TEM specimen preparation technique for solid state battery composites and other loosely bound samples. Ultramicroscopy 2024, 257 , 113904. https://doi.org/10.1016/j.ultramic.2023.113904
    8. John Donald Morley, Chandramohan George, Kathryn Hadler, Pablo R. Brito‐Parada. Crystallography of Active Particles Defining Battery Electrochemistry. Advanced Energy Materials 2024, 14 (6) https://doi.org/10.1002/aenm.202302893
    9. Jinhang Chen, Weiyin Chen, Bing Deng, Bowen Li, Carter Kittrell, James M. Tour. Cathode Interface Construction by Rapid Sintering in Solid‐State Batteries. Small 2024, 20 (8) https://doi.org/10.1002/smll.202307342
    10. Michael Malaki, Johannes Haust, Jean Philippe Beaupain, Henry Auer, Andreas Beyer, Katja Wätzig, Mihails Kusnezoff, Kerstin Volz. Probing the Interface Evolution in Co‐sintered All‐Phosphate Cathode‐Solid Electrolyte Composites. Advanced Materials Interfaces 2023, 10 (35) https://doi.org/10.1002/admi.202300513
    11. Chunli Li, Xinyu Zhang, Zhuolin Yang, Haijian Lv, Tinglu Song, Shijie Lu, Yuxiang Zhang, Tianwen Yang, Fan Xu, Feng Wu, Daobin Mu. Stable cycling of LiNi0.9Co0.05Mn0.05O2/lithium metal batteries enabled by synergistic tuning the surface stability of cathode/anode. Journal of Energy Chemistry 2023, 87 , 342-350. https://doi.org/10.1016/j.jechem.2023.08.033
    12. Jean Philippe Beaupain, Katja Waetzig, Henry Auer, Nicolas Zapp, Kristian Nikolowski, Mareike Partsch, Mihails Kusnezoff, Alexander Michaelis. Co-Sintering of Li1.3Al0.3Ti1.7(PO4)3 and LiFePO4 in Tape-Casted Composite Cathodes for Oxide Solid-State Batteries. Batteries 2023, 9 (11) , 543. https://doi.org/10.3390/batteries9110543
    13. Yingying Tan, Wanying Chang, Jinhai Cai, Yingjie Liu, Xiaoxue Tan, Chunyan Lai. Interface regulation strategies toward the challenges faced by cathode materials and solid electrolytes. Journal of Materials Science 2023, 58 (27) , 10911-10942. https://doi.org/10.1007/s10853-023-08691-1
    14. Thomas Demuth, Till Fuchs, Felix Walther, Anuj Pokle, Shamail Ahmed, Michael Malaki, Andreas Beyer, Jürgen Janek, Kerstin Volz. Influence of the sintering temperature on LLZO-NCM cathode composites for solid-state batteries studied by transmission electron microscopy. Matter 2023, 6 (7) , 2324-2339. https://doi.org/10.1016/j.matt.2023.04.022
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    ACS Applied Energy Materials

    Cite this: ACS Appl. Energy Mater. 2022, 5, 4, 4651–4663
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsaem.2c00084
    Published April 11, 2022
    Copyright © 2022 The Authors. Published by American Chemical Society
    Request reuse permissions

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