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Open AccessOpen Access JUSTC Chemistry 18 January 2023

A black phosphorus-graphite hybrid as a Li-ion regulator enabling stable lithium deposition

  • Hefei National Research Center for Physical Sciences at the Microscale and Department of Applied Chemistry, University of Science and Technology of China, Hefei 230026, China

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https://doi.org/10.52396/JUSTC-2022-0105
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  • Author Bio:

    Huanyu Xie is currently a postdoctoral fellow at the University of Science and Technology of China (USTC). He received his Ph.D. degree in Materials Science and Engineering from USTC in 2022 under the supervision of Prof. Hengxing Ji. He then joined Prof. Hengxing Ji’s group as a postdoctoral fellow in June 2022. His scientific interests include the protection and design of the anodes of lithium secondary batteries

    Chaonan Wang is presently a Ph.D. student in the Department of Applied Chemistry, University of Science and Technology of China (USTC). He received his bachelor’s degree from the School of Chemistry and Materials Science, USTC, in 2020. His research mainly focuses on the application of 2D materials in energy storage devices

    Hongchang Jin received his Ph.D. degree from the University of Science and Technology of China (USTC) in 2019 and is currently a postdoctoral researcher in USTC. His research mainly focuses on phosphorus-based anode materials for fast charging lithium-ion batteries

    Hengxing Ji has been a Professor at the School of Chemistry and Materials Science, University of Science and Technology of China (USTC), since 2013. He received his B.S. degree in 2003 from USTC and his Ph.D. degree in 2008 from the Institute of Chemistry, Chinese Academy of Sciences, under the supervision of Prof. Li-Jun Wan. He then joined Leibniz Institute for Solid State and Materials Research Dresden in 2008, working with Prof. Oliver G. Schmidt as a Humboldt research fellow before moving to the University of Texas at Austin in 2010, working with Prof. Rodney S. Ruoff as a postdoctoral researcher. His research interests include low-dimensional carbon nanostructures and micro/nanomaterials and devices for energy conversion and storage

  • Corresponding author: E-mail: jhckimi@ustc.edu.cn; E-mail: jihengx@ustc.edu.cn
  • Received Date: 22 July 2022
  • Accepted Date: 03 October 2022
    • Available Online: 18 January 2023
    Abstract

  • Abstract

    Lithium (Li) metal anodes have been regarded as the most promising candidates for high energy density secondary lithium batteries due to their high specific capacity and low redox potential. However, the issues of Li dendrites caused by nonuniform lithium deposition during battery cycling severely hinder the practical applications of Li metal anodes. Herein, a hybrid of black phosphorus-graphite (BP-G) is introduced to serve as an artificial protective layer for the Li metal anode. The two-dimensional few-layer BP, which is lithophilic, combined with the high electronic conductive graphite can act as a regulator to adjust the migration of Li ions, delivering a uniform and stable lithium deposition. As the growth of lithium dendrites is inhibited, the utilization of Li metal achieves > 98.5% for over 500 cycles in Li||Cu half cells, and the life span is maintained over 2000 h in Li||Li symmetric cells with a low voltage hysteresis of 50 mV. Moreover, the LiFePO4||Li full cell with a BP-G Li-ion regulator presents significantly better specific capacity and cycling stability than that with the bare Li metal anode. Therefore, the introduction of the BP-G Li-ion regulator is demonstrated to be an effective approach to enable stable lithium deposition for rechargeable Li metal batteries.

    Graphical abstract

    A black phosphorus-graphite hybrid acts as the Li-ion regulator, enabling stable lithium deposition.

    Abstract

    Lithium (Li) metal anodes have been regarded as the most promising candidates for high energy density secondary lithium batteries due to their high specific capacity and low redox potential. However, the issues of Li dendrites caused by nonuniform lithium deposition during battery cycling severely hinder the practical applications of Li metal anodes. Herein, a hybrid of black phosphorus-graphite (BP-G) is introduced to serve as an artificial protective layer for the Li metal anode. The two-dimensional few-layer BP, which is lithophilic, combined with the high electronic conductive graphite can act as a regulator to adjust the migration of Li ions, delivering a uniform and stable lithium deposition. As the growth of lithium dendrites is inhibited, the utilization of Li metal achieves > 98.5% for over 500 cycles in Li||Cu half cells, and the life span is maintained over 2000 h in Li||Li symmetric cells with a low voltage hysteresis of 50 mV. Moreover, the LiFePO4||Li full cell with a BP-G Li-ion regulator presents significantly better specific capacity and cycling stability than that with the bare Li metal anode. Therefore, the introduction of the BP-G Li-ion regulator is demonstrated to be an effective approach to enable stable lithium deposition for rechargeable Li metal batteries.

    • Public Summary

    • The hybrid of black phosphorus-graphite (BP-G) is introduced to serve as an artificial protective layer of a Li metal anode.
    • The utilization of Li metal achieves > 98.5% for over 500 cycles in Li||Cu half cells and the life span maintains over 2000 h in Li||Li symmetric cells with a low voltage hysteresis of 50 mV.
    • The LFP||Li full cell with BP-G Li-ion regulator offers a high specific capacity (162 mA∙h∙g-1 with 81% capacity retention until the 300th cycle).

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    • References(22)
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    Tang X, Zhou D, Li P, et al. MXene-based dendrite-free potassium metal batteries. Adv. Mater., 2020, 32 (4): 1906739. doi: 10.1002/adma.201906739
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    Figure  1.  Structure characterization. (a) Raman spectra, (b) TEM, and (c) HRTEM images of the BP-G hybrid. (d–f) TEM elemental mapping images of the BP-G hybrid. SEM images of the (g) (BP-G)/Li surface, (h) bare Li metal, and (i) cross section of (BP-G)/Li.

    Figure  2.  Li-ion transportation behaviors. (a) Tafel curves of the Li||Li symmetric cells with or without the BP-G layer to evaluate the exchange current densities. (b) Short circuit tests of Li||Cu half cells with bare Li or (BP-G)/Li metal anodes at 1.0 mA∙cm−2. Nyquist plots of Li||Li symmetric cells before and after polarization with the (c) bare Li and (d) (BP-G)/Li metal anodes; the corresponding direct current polarization curves of the (e) bare Li and (f) (BP-G)/Li metal anodes.

    Figure  3.  Electrochemical performances of Li||Cu half cells and Li||Li symmetric cells. (a) The variation of CE values in Li||Cu cells with the bare Li or (BP-G)/Li metal anodes at the current density of 1.0 mA∙cm−2 and areal capacity of 1.0 mA∙h∙cm−2. The corresponding charge/discharge curves at the (b) 50th and (c) 100th cycles. (d) Voltage profiles of Li||Li symmetric cells with the bare Li (orange line) and (BP-G)/Li (blue line) metal anodes at a current density of 1.0 mA∙cm−2 and an areal capacity of 1.0 mA∙h∙cm−2. The insets show the corresponding enlarged voltage profiles at different cycling stages. Impedance spectra of Li||Li symmetric cells with the bare Li or (BP-G)/Li metal anodes at (e) the initial state and the end of the (f) 100th and (g) 1000th cycles.

    Figure  4.  Electrochemical performances of LFP||Li full cells. (a) Variation in specific capacity retention with cycle numbers at 1.0 C. (b) Charge/discharge voltage profiles of the 10th and 300th cycles. Morphologies of lithium metal anodes after 300 cycles with the (c) bare Li or (d) (BP-G)/Li metal anodes.

    [1]
    Sheng L, Wang Q, Liu X, et al. Suppressing electrolyte-lithium metal reactivity via Li(+)-desolvation in uniform nano-porous separator. Nat. Commun., 2022, 13 (1): 172. doi: 10.1038/s41467-021-27841-0
    [2]
    Winter M, Barnett B, Xu K. Before Li ion batteries. Chem. Rev., 2018, 118 (23): 11433–11456. doi: 10.1021/acs.chemrev.8b00422
    [3]
    Wang M, Emre A E, Kim J Y, et al. Multifactorial engineering of biomimetic membranes for batteries with multiple high-performance parameters. Nat. Commun., 2022, 13 (1): 278. doi: 10.1038/s41467-021-27861-w
    [4]
    Yao Y X, Zhang X Q, Li B Q, et al. A compact inorganic layer for robust anode protection in lithium‐sulfur batteries. InfoMat, 2020, 2 (2): 379–388. doi: 10.1002/inf2.12046
    [5]
    Li J, Kong Z, Liu X, et al. Strategies to anode protection in lithium metal battery: A review. InfoMat, 2021, 3 (12): 1333–1363. doi: 10.1002/inf2.12189
    [6]
    Han Z, Zhang C, Lin Q, et al. A protective layer for lithium metal anode: Why and how. Small Methods, 2021, 5 (4): 2001035. doi: 10.1002/smtd.202001035
    [7]
    Ye Y, Zhao Y, Zhao T, et al. An Antipulverization and high-continuity lithium metal anode for high-energy lithium batteries. Adv. Mater., 2021, 33 (49): 2105029. doi: 10.1002/adma.202105029
    [8]
    Gao Y, Rojas T, Wang K, et al. Low-temperature and high-rate-charging lithium metal batteries enabled by an electrochemically active monolayer-regulated interface. Nat. Energy, 2020, 5 (7): 534–542. doi: 10.1038/s41560-020-0640-7
    [9]
    Wang Q, Yang C, Yang J, et al. Dendrite-free lithium deposition via a superfilling mechanism for high-performance Li-metal batteries. Adv. Mater., 2019, 31 (41): 1903248. doi: 10.1002/adma.201903248
    [10]
    Zheng J, Yan P, Mei D, et al. Highly stable operation of lithium metal batteries enabled by the formation of a transient high-concentration electrolyte layer. Adv. Energy Mater., 2016, 6 (8): 1502151. doi: 10.1002/aenm.201502151
    [11]
    Huang M, Yao Z, Yang Q, et al. Consecutive nucleation and confinement modulation towards Li plating in seeded capsules for durable Li-metal batteries. Angew. Chem. Int. Ed., 2021, 60 (25): 14040–14050. doi: 10.1002/anie.202102552
    [12]
    Xu Y, Zhou Y, Li T, et al. Multifunctional covalent organic frameworks for high capacity and dendrite-free lithium metal batteries. Energy Stor. Mater., 2020, 25: 334–341. doi: 10.1016/j.ensm.2019.10.005
    [13]
    Chang Z, Qiao Y, Yang H, et al. Sustainable lithium-metal battery achieved by a safe electrolyte based on recyclable and low-cost molecular sieve. Angew. Chem. Int. Ed., 2021, 60 (28): 15572–15581. doi: 10.1002/anie.202104124
    [14]
    Lange S, Schmidt P, Nilges T. Au3SnP7@ black phosphorus: An easy access to black phosphorus. Inorg. Chem., 2007, 46 (10): 4028–4035. doi: 10.1021/ic062192q
    [15]
    Sun J, Sun Y, Pasta M, et al. Entrapment of polysulfides by a black-phosphorus-modified separator for lithium-sulfur batteries. Adv. Mater., 2016, 28 (44): 9797–9803. doi: 10.1002/adma.201602172
    [16]
    Jin H, Xin S, Chuang C, et al. Black phosphorus composites with engineered interfaces for high-rate high-capacity lithium storage. Science, 2020, 370: 192–197. doi: 10.1126/science.aav5842
    [17]
    Zhao C Z, Chen P Y, Zhang R, et al. An ion redistributor for dendrite-free lithium metal anodes. Sci. Adv., 2018, 4 (11): eaat3446. doi: 10.1126/sciadv.aat3446
    [18]
    Chang Z, Qiao Y, Deng H, et al. A liquid electrolyte with de-solvated lithium ions for lithium-metal battery. Joule, 2020, 4 (8): 1776–1789. doi: 10.1016/j.joule.2020.06.011
    [19]
    He X, Jin S, Miao L, et al. A 3D hydroxylated MXene/carbon nanotubes composite as a scaffold for dendrite-free sodium-metal electrodes. Angew. Chem. Int. Ed., 2020, 59 (38): 16705–16711. doi: 10.1002/anie.202006783
    [20]
    Xie H, Hao Q, Jin H, et al. Redistribution of Li-ions using covalent organic frameworks towards dendrite-free lithium anodes: A mechanism based on a Galton Board. Sci. China Chem., 2020, 63 (9): 1306–1314. doi: 10.1007/s11426-020-9796-9
    [21]
    He Y, Chang Z, Wu S, et al. Simultaneously inhibiting lithium dendrites growth and polysulfides shuttle by a flexible MOF-based membrane in Li-S batteries. Adv. Energy Mater., 2018, 8 (34): 1802130. doi: 10.1002/aenm.201802130
    [22]
    Tang X, Zhou D, Li P, et al. MXene-based dendrite-free potassium metal batteries. Adv. Mater., 2020, 32 (4): 1906739. doi: 10.1002/adma.201906739
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