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

Interface Instability in LiFePO4–Li3+xP1–xSixO4 All-Solid-State Batteries

Cite this: Chem. Mater. 2018, 30, 17, 5886–5895
Publication Date (Web):July 25, 2018
Copyright © 2018 American Chemical Society

    Article Views





    Other access options
    Supporting Info (1)»


    Abstract Image

    All-solid-state batteries (ASSBs) based on noncombustible solid electrolytes are promising candidates for safe and high energy storage systems, but it remains a challenge to prepare systems with stable interfaces between the various solid components that survive both the synthesis conditions and electrochemical cycling. We have investigated cathode mixtures based on a carbon-coated LiFePO4 active material and Li3+xP1–xSixO4 solid electrolyte for potential use in all-solid-state batteries. Half-cells were constructed by combining both compounds into pellets by spark plasma sintering (SPS). We report the fast and quantitative formation of two solid solutions (LiFePO4–Fe2SiO4 and Li3PO4–Li2FeSiO4) for different compositions and ratios of the pristine compounds, as tracked by powder X-ray diffraction and solid-state nuclear magnetic resonance; X-ray absorption near-edge spectroscopy confirms the formation of iron silicates similar to Fe2SiO4. Scanning electron microscopy and energy dispersive X-ray spectroscopy reveal diffusion of iron cations up to 40 μm into the solid electrolyte even in the short processing times accessible by SPS. Electrochemical cycling of the SPS-treated cathode mixtures demonstrates a substantial decrease in capacity following the formation of the solid solutions during sintering. Consequently, all-solid-state batteries based on LiFePO4 and Li3+xP1–xSixO4 would necessitate iron ion blocking layers. More generally, this study highlights the importance of systematic studies on the fundamental reactions at the active material–solid electrolyte interfaces to enable the introduction of protective layers for commercially successful ASSBs.

    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.8b01746.

    • Table of refined lattice parameters; Rietveld refinements of X-ray diffractograms of starting materials and reference samples; comparisons of X-ray diffractograms and 31P MAS NMR measurements; visualization of the local environment of the phosphorus atoms in P-doped Li2FeSiO4 (Pmnb) and in LiFePO4; galvanostatic profiles (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 21 publications.

    1. Elias Sebti, Hayden A. Evans, Hengning Chen, Peter M. Richardson, Kelly M. White, Raynald Giovine, Krishna Prasad Koirala, Yaobin Xu, Eliovardo Gonzalez-Correa, Chongmin Wang, Craig M. Brown, Anthony K. Cheetham, Pieremanuele Canepa, Raphaële J. Clément. Stacking Faults Assist Lithium-Ion Conduction in a Halide-Based Superionic Conductor. Journal of the American Chemical Society 2022, 144 (13) , 5795-5811.
    2. Toyoki Okumura, Tomonari Takeuchi, Hironori Kobayashi. All-Solid-State Batteries with LiCoO2-Type Electrodes: Realization of an Impurity-Free Interface by Utilizing a Cosinterable Li3.5Ge0.5V0.5O4 Electrolyte. ACS Applied Energy Materials 2021, 4 (1) , 30-34.
    3. Yukihiro Okuno, Jun Haruyama, Yoshitaka Tateyama. Comparative Study on Sulfide and Oxide Electrolyte Interfaces with Cathodes in All-Solid-State Battery via First-Principles Calculations. ACS Applied Energy Materials 2020, 3 (11) , 11061-11072.
    4. Toyoki Okumura, Sou Taminato, Yoshinobu Miyazaki, Michinori Kitamura, Tomohiro Saito, Tomonari Takeuchi, Hironori Kobayashi. LISICON-Based Amorphous Oxide for Bulk-Type All-Solid-State Lithium-Ion Battery. ACS Applied Energy Materials 2020, 3 (4) , 3220-3229.
    5. Kelsey B. Hatzell, Xi Chelsea Chen, Corie L. Cobb, Neil P. Dasgupta, Marm B. Dixit, Lauren E. Marbella, Matthew T. McDowell, Partha P. Mukherjee, Ankit Verma, Venkatasubramanian Viswanathan, Andrew S. Westover, Wolfgang G. Zeier. Challenges in Lithium Metal Anodes for Solid-State Batteries. ACS Energy Letters 2020, 5 (3) , 922-934.
    6. Honggang He, Litong Wang, Malek Al‐Abbasi, Chunyan Cao, Heng Li, Zhu Xu, Shi Chen, Wei Zhang, Ruiqing Li, Yuekun Lai, Yuxin Tang, Mingzheng Ge. Interface Engineering on Constructing Physical and Chemical Stable Solid‐State Electrolyte Toward Practical Lithium Batteries. ENERGY & ENVIRONMENTAL MATERIALS 2024, 120
    7. Lei Zhang, Huilin Fan, Yuzhen Dang, Quanchao Zhuang, Hamidreza Arandiyan, Yuan Wang, Ningyan Cheng, Hongyu Sun, H. Hugo Pérez Garza, Runguo Zheng, Zhiyuan Wang, Sajjad S. Mofarah, Pramod Koshy, Suresh K. Bhargava, Yanhua Cui, Zongping Shao, Yanguo Liu. Recent advances in in situ and operando characterization techniques for Li 7 La 3 Zr 2 O 12 -based solid-state lithium batteries. Materials Horizons 2023, 10 (5) , 1479-1538.
    8. Ronghao Wang, Kaiwen Sun, Yuhao Zhang, Bingqin Li, Chengfei Qian, Jingfa Li, Fangyang Liu, Weizhai Bao. Nanoscale interface engineering of inorganic Solid-State electrolytes for High-Performance alkali metal batteries. Journal of Colloid and Interface Science 2022, 621 , 41-66.
    9. Maoyu Wang, Zhenxing Feng. Interfacial processes in electrochemical energy systems. Chemical Communications 2021, 57 (81) , 10453-10468.
    10. Marcos Lucero, Shen Qiu, Zhenxing Feng. In situ characterizations of solid–solid interfaces in solid‐state batteries using synchrotron X‐ray techniques. Carbon Energy 2021, 3 (5) , 762-783.
    11. Mei-Chin Pang, Kai Yang, Rowena Brugge, Teng Zhang, Xinhua Liu, Feng Pan, Shichun Yang, Ainara Aguadero, Billy Wu, Monica Marinescu, Huizhi Wang, Gregory J. Offer. Interactions are important: Linking multi-physics mechanisms to the performance and degradation of solid-state batteries. Materials Today 2021, 49 , 145-183.
    12. Lingzi Sang, Nicholas Kissoon, Fuwei Wen. Characterizations of dynamic interfaces in all-solid lithium batteries. Journal of Power Sources 2021, 506 , 229871.
    13. Ziteng Liang, Yuxuan Xiang, Dawei Wang, Riqiang Fu, Yong Yang. NMR Studies of Oxide-type Solid State Electrolytes in All Solid State Batteries. 2021, 297-322.
    14. Hongchun Wang, Jianping Zhu, Yu Su, Zhengliang Gong, Yong Yang. Interfacial compatibility issues in rechargeable solid-state lithium metal batteries: a review. Science China Chemistry 2021, 64 (6) , 879-898.
    15. Toyoki Okumura, Yoshitaka Shiba, Noriko Sakamoto, Takeshi Kobayashi, Saori Hashimoto, Kentaro Doguchi, Harunobu Ogaki, Tomonari Takeuchi, Hironori Kobayashi. Zr- and Ce-doped Li 6 Y(BO 3 ) 3 electrolyte for all-solid-state lithium-ion battery. RSC Advances 2021, 11 (27) , 16530-16536.
    16. Yan-Yun Sun, Feng Li, Pei-Yu Hou. Research progress on the interfaces of solid-state lithium metal batteries. Journal of Materials Chemistry A 2021, 9 (15) , 9481-9505.
    17. Shuaifeng Lou, Fang Zhang, Chuankai Fu, Ming Chen, Yulin Ma, Geping Yin, Jiajun Wang. Interface Issues and Challenges in All‐Solid‐State Batteries: Lithium, Sodium, and Beyond. Advanced Materials 2021, 33 (6)
    18. Yong Chen, Kaihua Wen, Tianhua Chen, Xiaojing Zhang, Michel Armand, Shimou Chen. Recent progress in all-solid-state lithium batteries: The emerging strategies for advanced electrolytes and their interfaces. Energy Storage Materials 2020, 31 , 401-433.
    19. Zheng-Yang Hu, Zhao-Hui Zhang, Xing-Wang Cheng, Fu-Chi Wang, Yi-Fan Zhang, Sheng-Lin Li. A review of multi-physical fields induced phenomena and effects in spark plasma sintering: Fundamentals and applications. Materials & Design 2020, 191 , 108662.
    20. Yuxuan Xiang, Xia Li, Yongqiang Cheng, Xueliang Sun, Yong Yang. Advanced characterization techniques for solid state lithium battery research. Materials Today 2020, 36 , 139-157.
    21. Theodosios Famprikis, Pieremanuele Canepa, James A. Dawson, M. Saiful Islam, Christian Masquelier. Fundamentals of inorganic solid-state electrolytes for batteries. Nature Materials 2019, 18 (12) , 1278-1291.

    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