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Open AccessOpen Access JUSTC Chemistry 18 January 2023

A deformable spinel-type chloride cathode with high ionic conductivity for all-solid-state Li batteries

  • Department of Materials Science & Engineering, University of Science and Technology of China, Hefei 230026, China

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https://doi.org/10.52396/JUSTC-2022-0071
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  • Author Bio:

    Jipeng Hao is currently a master’s student of University of Science and Technology of China (USTC). He received his Bachelor’s degree from Southeast University (SEU) in 2019. His main research interests focus on all-solid-state batteries, halide solid state electrolytes and novel cathode active materials

    Cheng Ma received his B.S. degree in Materials Science and Engineering in 2006 from Tsinghua University (Beijing, China) and Ph.D. degree in Materials Science and Engineering in 2012 from Iowa State University. After completing his work as a postdoctoral researcher at the Oak Ridge National Laboratory in 2016, he joined the University of Science and Technology of China as a Professor. His research interests include the critical materials and interfaces in all-solid-state Li batteries

  • Corresponding author: E-mail: mach16@ustc.edu.cn
  • Received Date: 23 April 2022
  • Accepted Date: 30 May 2022
    • Available Online: 18 January 2023
    Abstract

  • Abstract

    All-solid-state Li batteries (ASSLBs) are now considered to be next-generation energy storage devices due to their advantages in safety and energy density. With liquid electrolytes replaced by solid electrolytes, novel cathode active materials (CAMs) with different characteristics are needed. The solid-solid contact in ASSLBs requires CAMs to have good deformability. In addition, higher ionic conductivity is also essential to reduce the mass of the Li-ion conductive agent, thus accessing a higher overall capacity. Herein, we report a spinel-type chloride cathode Li2−2xMn1−xZrxCl4, which has good deformability and high ionic conductivity (up to 0.16 mS∙cm−1 at 25 °C). The ASSLB using the optimal composition of LiMn0.5Zr0.5Cl4 as the cathode exhibits promising cycling stability for 200 cycles at room temperature.

    Graphical abstract

    Zr4+-doped spinel-type chloride Li2-2xMn1-xZrxCl4 exhibits high ionic conductivity and promising cycling stability.

    Abstract

    All-solid-state Li batteries (ASSLBs) are now considered to be next-generation energy storage devices due to their advantages in safety and energy density. With liquid electrolytes replaced by solid electrolytes, novel cathode active materials (CAMs) with different characteristics are needed. The solid-solid contact in ASSLBs requires CAMs to have good deformability. In addition, higher ionic conductivity is also essential to reduce the mass of the Li-ion conductive agent, thus accessing a higher overall capacity. Herein, we report a spinel-type chloride cathode Li2−2xMn1−xZrxCl4, which has good deformability and high ionic conductivity (up to 0.16 mS∙cm−1 at 25 °C). The ASSLB using the optimal composition of LiMn0.5Zr0.5Cl4 as the cathode exhibits promising cycling stability for 200 cycles at room temperature.

    • Public Summary

    • A series of deformable spinel-type chloride cathodes Li2-2xMn1-xZrxCl4 were synthesized by mechanical ball milling.
    • The Zr4+-doped Li2-2xMn1-xZrxCl4 exhibits high ionic conductivity and low activation energy, which was confirmed by electrochemical impedance spectroscopy.
    • The optimal composition LiMn0.5Zr0.5Cl4 was integrated as the cathode into all-solid-state cells, and a promising cycling stability for 200 cycles was achieved.

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    • References(22)
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    Janek J, Zeier W G. A solid future for battery development. Nature Energy, 2016, 1: 16141. doi: 10.1038/nenergy.2016.141
    [2]
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    [21]
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    Figure  1.  (a) XRD patterns of as-milled Li2−2xMn1−xZrxCl4. (b) Partial enlarged image of (a).

    Figure  2.  XRD patterns of the 350 °C-annealed Li2−2xMn1−xZrxCl4 powder samples.

    Figure  3.  Conductivity of LMZC5 under different processing conditions. (a, b) Nyquist plots of the as-milled (a) and 350 °C-annealed (b) LMZC5 at 25 °C. (c, d) Chronoamperometry results for the as-milled (c) and 350 °C-annealed (d) LMZC5 at 25 °C with a voltage step of 1 V.

    Figure  4.  Conductivity and activation energy evolution upon Zr4+ substitution. (a) Arrhenius plots of Li+ conductivity for as-milled Li2−2xMn1−xZrxCl4. (b) Ionic conductivities at 25 °C and activation energies of as-milled Li2-2xMn1-xZrxCl4.

    Figure  5.  Thermodynamic equilibrium voltage profiles and the phase equilibria for LMZC5 based on DFT calculations.

    Figure  6.  LSV curves of the Li/Li6PS5Cl-LMZC5/LMZC5+C cell at 0.1 mV∙s−1. The measurements were conducted at room temperature. (a) 0–3.1 V. (b) 3–5 V.

    Figure  7.  Electrochemical performance of the Li-In/Li6PS5Cl-LIC/LMZC5 cell at 25 °C. (a) Charge and discharge profiles at 0.1 C. (b) Rate performance. (c) Long-term cycling performance at 0.1 C.

    Figure  8.  (a) Ex situ XRD patterns of LMZC5 at different depths of discharge (DoDs). The DoD of each XRD pattern is indicated in (b). (b) The initial discharge profile at 0.1 C, with the DoD for each XRD pattern in (a) indicated.

    [1]
    Janek J, Zeier W G. A solid future for battery development. Nature Energy, 2016, 1: 16141. doi: 10.1038/nenergy.2016.141
    [2]
    Li J, Ma C, Chi M, et al. Solid electrolyte: The key for high-voltage lithium batteries. Advanced Energy Materials, 2015, 5: 1401408. doi: 10.1002/aenm.201401408
    [3]
    Xia S, Wu X, Zhang Z, et al. Practical challenges and future perspectives of all-solid-state lithium-metal batteries. Chem, 2019, 5: 753–785. doi: 10.1016/j.chempr.2018.11.013
    [4]
    Albertus P, Anandan V, Ban C, et al. Challenges for and pathways toward Li-metal-based all-solid-state batteries. ACS Energy Letters, 2021, 6: 1399–1404. doi: 10.1021/acsenergylett.1c00445
    [5]
    Gao X, Liu B, Hu B, et al. Solid-state lithium battery cathodes operating at low pressures. Joule, 2022, 6: 636–646. doi: 10.1016/j.joule.2022.02.008
    [6]
    Tanibata N, Kato M, Takimoto S, et al. High formability and fast lithium diffusivity in metastable spinel chloride for rechargeable all-solid-state lithium-ion batteries. Advanced Energy and Sustainability Research, 2020, 1: 2000025. doi: 10.1002/aesr.202000025
    [7]
    Zhao Q, Stalin S, Zhao C Z, et al. Designing solid-state electrolytes for safe, energy-dense batteries. Nature Reviews Materials, 2020, 5: 229–252. doi: 10.1038/s41578-019-0165-5
    [8]
    Nitta N, Wu F, Lee J T, et al. Li-ion battery materials: present and future. Materials Today, 2015, 18: 252–264. doi: 10.1016/j.mattod.2014.10.040
    [9]
    Ellis B L, Lee K T, Nazar L F. Positive electrode materials for Li-ion and Li-batteries. Chemistry of Materials, 2010, 22: 691–714. doi: 10.1021/cm902696j
    [10]
    Cros C, Hanebali L, Latie´ L, et al. Structure, ionic motion and conductivity in some solid-solutions of the LiCl-MCl2 systems (M=Mg, V, Mn). Solid State Ionics, 1983, 9-10: 139–147. doi: 10.1016/0167-2738(83)90223-0
    [11]
    Kanno R, Takeda Y, Takada K, et al. Ionic conductivity and phase transition of the spinel system Li2−2 xM1+ xCl4 (M=Mg, Mn, Cd). Journal of The Electrochemical Society, 1984, 131: 469–474. doi: 10.1149/1.2115611
    [12]
    Han F, Zhu Y, He X, et al. Electrochemical stability of Li10GeP2S12 and Li7La3Zr2O12 solid electrolytes. Advanced Energy Materials, 2016, 6: 1501590. doi: 10.1002/aenm.201501590
    [13]
    van Loon C J J, de Jong J. Some chlorides with the inverse spinel structure. Acta Crystallographica Section B:Structural Science, Crystal Engineering and Materials, 1975, 31: 2549–2550. doi: 10.1107/S0567740875008114
    [14]
    Li X N, Liang J W, Luo J, et al. Air-stable Li3InCl6 electrolyte with high voltage compatibility for all-solid-state batteries. Energy & Environmental Science, 2019, 12: 2665–2671. doi: 10.1039/c9ee02311a
    [15]
    Liang J, Li X, Wang S, et al. Site-occupation-tuned superionic Li xScCl3+ x halide solid electrolytes for all-solid-state batteries. Journal of the American Chemical Society, 2020, 142: 7012–7022. doi: 10.1021/jacs.0c00134
    [16]
    Wang K, Ren Q, Gu Z, et al. A cost-effective and humidity-tolerant chloride solid electrolyte for lithium batteries. Nature Communications, 2021, 12: 4410. doi: 10.1038/s41467-021-24697-2
    [17]
    Kwak H, Han D, Lyoo J, et al. New cost-effective halide solid electrolytes for all-solid-state batteries: Mechanochemically prepared Fe3+-substituted Li2ZrCl6. Advanced Energy Materials, 2021, 11: 2003190. doi: 10.1002/aenm.202003190
    [18]
    Asano T, Sakai A, Ouchi S, et al. Solid halide electrolytes with high lithium-ion conductivity for application in 4 V class bulk-type all-solid-state batteries. Advanced Materials, 2018, 30: 1803075. doi: 10.1002/adma.201803075
    [19]
    Zhu Y Z, He X F, Mo Y F. Origin of outstanding stability in the lithium solid electrolyte materials: insights from thermodynamic analyses based on first-principles calculations. ACS Applied Materials & Interfaces, 2015, 7: 23685–23693. doi: 10.1021/acsami.5b07517
    [20]
    Ong S P, Wang L, Kang B, et al. Li−Fe−P−O2 phase diagram from first principles calculations. Chemistry of Materials, 2008, 20: 1798–1807. doi: 10.1021/cm702327g
    [21]
    Mo Y, Ong S P, Ceder G. First principles study of the Li10GeP2S12 lithium super ionic conductor material. Chemistry of Materials, 2012, 24: 15–17. doi: 10.1021/cm203303y
    [22]
    Jain A, Ong S P, Hautier G, et al. Commentary: The Materials Project: A materials genome approach to accelerating materials innovation. APL Materials, 2013, 1: 011002. doi: 10.1063/1.4812323
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