ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Highly Reversible Conversion-Type FeOF Composite Electrode with Extended Lithium Insertion by Atomic Layer Deposition LiPON Protection

View Author Information
Department of Materials Science and Engineering, University of Maryland, College Park, Maryland 20742, United States
Institute for Systems Research, University of Maryland, College Park, Maryland 20740, United States
§ Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, Maryland 20740, United States
Department of Chemistry, Bar-Ilan University, Ramat Gan 52900, Israel
Department of Materials and Interfaces, Weizmann Institute of Science, Rehovot 76100, Israel
# AIM Laboratory, Nano Center, University of Maryland, College Park, Maryland 20742, United States
@ Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, United States
Cite this: Chem. Mater. 2017, 29, 20, 8780–8791
Publication Date (Web):September 28, 2017
Copyright © 2017 American Chemical Society

    Article Views





    Other access options
    Supporting Info (1)»


    Abstract Image

    High-energy conversion electrodes undergo successive Li insertion and conversion during lithiation. A primary scientific obstacle to harnessing the potentially high lithium storage capabilities of conversion electrode materials has been the formation of insulating new phases throughout the conversion reactions. These new phases are chemically stable, and electrochemically irreversible if formed in large amounts with coarsening. Herein, we synthesized FeOF conversion material as a model system and mechanistically demonstrate that a thin solid electrolyte [lithium phosphorus oxynitride (LiPON)] atomic layer deposition-deposited on the composite electrode extends the Li insertion process to higher concentrations, delaying the onset of a parasitic chemical conversion reaction and rendering the redox reaction of the protected conversion electrode electrochemically reversible. Reversibility is demonstrated to at least 100 cycles, with the LiPON protective coating increasing capacity retention from 29 to 89% at 100 cycles. Pursuing the chemical mechanism behind the boosted electrochemical reversibility, we conducted electron energy-loss spectroscopy, X-ray photoelectron spectroscopy, solid-state nuclear magnetic resonance, and electrochemical measurements that unrevealed the suppression of undesired phase formation and extended lithium insertion of the coated electrode. Support for the delayed consequences of the conversion reaction is also obtained by high-resolution transmission electron microscopy. Our findings strongly suggest that undesired new phase formation upon lithiation of electrode materials can be suppressed in the presence of a thin protection layer not only on the surface of the coated electrode but also in the bulk of the material through mechanical confinement that modulates the electrochemical reaction.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.


    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.7b03058.

    • Additional experimental methods and details, XRD data, XPS spectrum, TEM micrographs, solid-state NMR description, and cyclic voltammograms (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 40 publications.

    1. Milad Madadi, Mari Heikkinen, Anish Philip, Maarit Karppinen. Conformal High-Aspect-Ratio Solid Electrolyte Thin Films for Li-Ion Batteries by Atomic Layer Deposition. ACS Applied Electronic Materials 2024, 6 (3) , 1574-1580.
    2. Binh Hoang, Victoria Castagna Ferrari, Haotian Wang, David M Stewart, Roya Damircheli, Chuan-Fu Lin. From Amorphous to Crystalline Thin-Film FeF3 Conversion Electrodes by Sputtering Deposition. ACS Applied Energy Materials 2023, 6 (19) , 10005-10011.
    3. Zach Levy, Victoria Castagna Ferrari, Pablo Rosas, Mitchell J. Walker, Kalpak Duddella, Micah Haseman, David Stewart, Gary Rubloff, Leonard J. Brillson. Lithium Spatial Distribution and Split-Off Electronic Bands at Nanoscale V2O5/LiPON Interfaces. ACS Applied Energy Materials 2023, 6 (9) , 4538-4548.
    4. Venkataraman Thangadurai, Bowen Chen. Solid Li- and Na-Ion Electrolytes for Next Generation Rechargeable Batteries. Chemistry of Materials 2022, 34 (15) , 6637-6658.
    5. Minji Lee, Waheed Ahmad, Dae Woong Kim, Kyu Moon Kwon, Ha Yeon Kwon, Han-Bin Jang, Seung-Won Noh, Dae-Ho Kim, Syed Jazib Abbas Zaidi, Hwiyeol Park, Heung Chan Lee, Muhammad Abdul Basit, Tae Joo Park. Powder Coatings via Atomic Layer Deposition for Batteries: A Review. Chemistry of Materials 2022, 34 (8) , 3539-3587.
    6. Milad Madadi, Juho Heiska, Jenna Multia, Maarit Karppinen. Atomic and Molecular Layer Deposition of Alkali Metal Based Thin Films. ACS Applied Materials & Interfaces 2021, 13 (48) , 56793-56811.
    7. Jed D. LaCoste, Andriy Zakutayev, Ling Fei. A Review on Lithium Phosphorus Oxynitride. The Journal of Physical Chemistry C 2021, 125 (7) , 3651-3667.
    8. Xinyu Zhang, Eleni Temeche, Richard M. Laine. Design, Synthesis, and Characterization of Polymer Precursors to LixPON and LixSiPON Glasses: Materials That Enable All-Solid-State Batteries (ASBs). Macromolecules 2020, 53 (7) , 2702-2712.
    9. Joshua P. Pender, Gaurav Jha, Duck Hyun Youn, Joshua M. Ziegler, Ilektra Andoni, Eric J. Choi, Adam Heller, Bruce S. Dunn, Paul S. Weiss, Reginald M. Penner, C. Buddie Mullins. Electrode Degradation in Lithium-Ion Batteries. ACS Nano 2020, 14 (2) , 1243-1295.
    10. Gang Wang, Xunhui Xiong, Dong Xie, Xiangxiang Fu, Zhihua Lin, Chenghao Yang, Kaili Zhang, Meilin Liu. A Scalable Approach for Dendrite-Free Alkali Metal Anodes via Room-Temperature Facile Surface Fluorination. ACS Applied Materials & Interfaces 2019, 11 (5) , 4962-4968.
    11. Olivier J. Hernandez, Gregory Geneste, Takeshi Yajima, Yoji Kobayashi, Masatoshi Okura, Kouhei Aidzu, Cédric Tassel, Serge Paofai, Diptikanta Swain, Clemens Ritter, Hiroshi Kageyama. Site Selectivity of Hydride in Early-Transition-Metal Ruddlesden–Popper Oxyhydrides. Inorganic Chemistry 2018, 57 (17) , 11058-11067.
    12. Chuan-Fu Lin, Yue Qi, Keith Gregorczyk, Sang Bok Lee, and Gary W. Rubloff . Nanoscale Protection Layers To Mitigate Degradation in High-Energy Electrochemical Energy Storage Systems. Accounts of Chemical Research 2018, 51 (1) , 97-106.
    13. Hongyan Zhou, Yanming Zhao, Yunbo Li, Quan Kuang, Youzhong Dong, Qinghua Fan. Interface engineering of FeOF/FeF2 heterostructure for ultrastable Li-ion/Na-ion storage. Journal of Power Sources 2024, 592 , 233911.
    14. Xiangbo Meng. Interface engineering of lithium metal anodes via atomic and molecular layer deposition. Inorganic Chemistry Frontiers 2024, 11 (3) , 659-681.
    15. Md Raziun Bin Mamtaz, Xavier Michaud, Hongseok Jo, Simon S. Park. Stress and Manufacturability in Solid-State Lithium-Ion Batteries. International Journal of Precision Engineering and Manufacturing-Green Technology 2023, 10 (4) , 1093-1137.
    16. Dong Yan, Hui Ying Yang, Ying Bai. Tactics to optimize conversion-type metal fluoride/sulfide/oxide cathodes toward advanced lithium metal batteries. Nano Research 2023, 16 (6) , 8173-8190.
    17. Jun Li, Xifei Li, Xiangyang Li, Qinting Jiang. Toward High Energy Density FeF x ( x =2 and 3) Cathodes for Lithium‐Ion Batteries. Batteries & Supercaps 2023, 6 (4)
    18. Lidong Sun, Yu Li, Wei Feng. Metal Fluoride Cathode Materials for Lithium Rechargeable Batteries: Focus on Iron Fluorides. Small Methods 2023, 7 (2)
    19. Xiangbo Meng, Zonghai Chen. Constituting robust interfaces for better lithium-ion batteries and beyond using atomic and molecular layer deposition. 2023, 649-663.
    20. Jaehoon Heo, Sung-Kyun Jung, Insang Hwang, Sung-Pyo Cho, Donggun Eum, Hyeokjun Park, Jun-Hyuk Song, Seungju Yu, Kyungbae Oh, Giyun Kwon, Taehyun Hwang, Kun-Hee Ko, Kisuk Kang. Amorphous iron fluorosulfate as a high-capacity cathode utilizing combined intercalation and conversion reactions with unexpectedly high reversibility. Nature Energy 2023, 8 (1) , 30-39.
    21. Jingru Zhai, Zhengyu Lei, Kening Sun, Shengcai Zhu. MXene enabled binder-free FeOF cathode with high volumetric and gravimetric capacities for flexible lithium ion batteries. Electrochimica Acta 2022, 423 , 140595.
    22. Linhua Li, Liangshun Xiang, Yan Lin, Lei Chen, Renqing Guo, Yiqi Cao, Xiaohua Huang, Jianbo Wu. Li/Na Ion Storage Performance of a FeOF Nano Rod with Controllable Morphology. Processes 2022, 10 (8) , 1491.
    23. Ryota FURUYA, Nobuyuki SERIZAWA, Yasushi KATAYAMA. Potential Dependence of the Impedance of Solid Electrolyte Interphase in Some Electrolytes. Electrochemistry 2022, 90 (5) , 057002-057002.
    24. Lowie Henderick, Arpan Dhara, Andreas Werbrouck, Jolien Dendooven, Christophe Detavernier. Atomic layer deposition of metal phosphates. Applied Physics Reviews 2022, 9 (1)
    25. Yongqiang Liu, Xin Wang, Sujan Kumar Ghosh, Min Zou, Hua Zhou, Xianghui Xiao, Xiangbo Meng. Atomic layer deposition of lithium zirconium oxides for the improved performance of lithium-ion batteries. Dalton Transactions 2022, 51 (7) , 2737-2749.
    26. Edy Riyanto, Erie Martides, Ghalya Pikra, Tinton Dwi Atmaja, Rakhmad Indra Pramana, Andri Joko Purwanto, Arifin Santosa, Endro Junianto, Rudi Darussalam, Aep Saepudin, Anjar Susatyo, Ridwan Arief Subekti, Yusuf Suryo Utomo, Dalmasius Ganjar Subagio, Ahmad Fudholi, Haznan Abimanyu, Yadi Radiansah, Henny Sudibyo, Kusnadi, Ahmad Rajani, Suprapto, Budi Prawara. A review of atomic layer deposition for high lithium-ion battery performance. Journal of Materials Research and Technology 2021, 15 , 5466-5481.
    27. Tripurari Sharan Tripathi, Maarit Karppinen. Mixed‐Anion Compounds: An Unexplored Playground for ALD Fabrication. Advanced Materials Interfaces 2021, 8 (11)
    28. Xiangbo Meng. Atomic and molecular layer deposition in pursuing better batteries. Journal of Materials Research 2021, 36 (1) , 2-25.
    29. Xiangbo Meng. Atomic layer deposition of solid-state electrolytes for next-generation lithium-ion batteries and beyond: Opportunities and challenges. Energy Storage Materials 2020, 30 , 296-328.
    30. Xiangyu Zhao, Zhirong Zhao‐Karger, Maximilian Fichtner, Xiaodong Shen. Halogenid‐basierte Materialien und Chemie für wiederaufladbare Batterien. Angewandte Chemie 2020, 132 (15) , 5954-6004.
    31. Xiangyu Zhao, Zhirong Zhao‐Karger, Maximilian Fichtner, Xiaodong Shen. Halide‐Based Materials and Chemistry for Rechargeable Batteries. Angewandte Chemie International Edition 2020, 59 (15) , 5902-5949.
    32. Fan Yu, Lei Du, Gaixia Zhang, Fengmei Su, Weichao Wang, Shuhui Sun. Electrode Engineering by Atomic Layer Deposition for Sodium‐Ion Batteries: From Traditional to Advanced Batteries. Advanced Functional Materials 2020, 30 (9)
    33. Mingjie Du, Kaiming Liao, Qian Lu, Zongping Shao. Recent advances in the interface engineering of solid-state Li-ion batteries with artificial buffer layers: challenges, materials, construction, and characterization. Energy & Environmental Science 2019, 12 (6) , 1780-1804.
    34. Jingru Zhai, Zhengyu Lei, Kening Sun. 3D Starfish‐Like FeOF on Graphene Sheets: Engineered Synthesis and Lithium Storage Performance. Chemistry – A European Journal 2019, 25 (32) , 7733-7739.
    35. Xiaopeng Li, Yongzhi Zhang, Yan Meng, Yujue Wang, Guangqun Tan, Hongyan Yuan, Dan Xiao. Three-dimensional iron oxyfluoride/N-doped carbon hybrid nanocomposites as high-performance cathodes for rechargeable Li-ion batteries. Inorganic Chemistry Frontiers 2019, 6 (2) , 465-472.
    36. Sungkyu Kim, Guennadi Evmenenko, Yaobin Xu, Donald Bruce Buchholz, Michael Bedzyk, Kai He, Jinsong Wu, Vinayak P. Dravid. Thin Film RuO 2 Lithiation: Fast Lithium‐Ion Diffusion along the Interface. Advanced Functional Materials 2018, 28 (52)
    37. Chilin Li, Keyi Chen, Xuejun Zhou, Joachim Maier. Electrochemically driven conversion reaction in fluoride electrodes for energy storage devices. npj Computational Materials 2018, 4 (1)
    38. Kaiyuan Wei, Yu Zhao, Yixiu Cui, Jiali Wang, Yanhua Cui, Rongtao Zhu, Quanchao Zhuang, Mingzhe Xue. Lithium phosphorous oxynitride (LiPON) coated NiFe2O4 anode material with enhanced electrochemical performance for lithium ion batteries. Journal of Alloys and Compounds 2018, 769 , 110-119.
    39. Brecht Put, Philippe M. Vereecken, Andre Stesmans. On the chemistry and electrochemistry of LiPON breakdown. Journal of Materials Chemistry A 2018, 6 (11) , 4848-4859.
    40. Liwei Zhao, Ayuko Kitajou, Shigeto Okada. Thermal Characteristics of Conversion-Type FeOF Cathode in Li-ion Batteries. Batteries 2017, 3 (4) , 33.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Your Mendeley pairing has expired. Please reconnect