Journal of Sol-Gel Science and Technology

, Volume 89, Issue 1, pp 303–309 | Cite as

Preparation of lithium ion conductive Li6PS5Cl solid electrolyte from solution for the fabrication of composite cathode of all-solid-state lithium battery

  • Nataly Carolina Rosero-Navarro
  • Akira Miura
  • Kiyoharu TadanagaEmail author
Original Paper: Sol–gel and hybrid materials for energy, environment and building applications


An argyrodite type Li6PS5Cl was prepared by the solution process using a mixture of solvents with a fast evaporation rate. The crystal phase and ionic conductivity of the Li6PS5Cl solid electrolyte were examined by X-ray diffraction and electrochemical impedance spectroscopy, respectively. Li6PS5Cl derived from solution process shows an argyrodite structure with an ionic conductivity of 6 × 10-5 S cm−1 at room temperature. Composite cathode was directly prepared by dispersing LiNi1/3Mn1/3Co1/3O2 (84 wt%) and a conductive additive (2 wt%) into a Li6PS5Cl precursor solution (14 wt%), with subsequent heating at 150 °C. Morphology of the composite cathode was evaluated by scanning electron microscopy and energy-dispersive X-ray spectroscopy. The formation of Li6PS5Cl-layer on the active material particles was observed. A bulk-type all-solid-state cell was fabricated with composite cathode derived from the solution process, achieving an initial discharge capacity of 160 mAh g−1 and capacity retention of ~80% after 20 cycles with a capacity efficiency of 100%.

Argyrodite type Li6PS5Cl prepared by solution process and its application to prepare composite cathode for an all-solid-state lithium battery.


  • An argyrodite type Li6PS5Cl was prepared by solution process using a mixture solvents with a fast evaporation rate.

  • Composite cathode for all solid state battery was directly prepared by dispersing a cathode material in the precursor solution.

  • The cell worked as a rechargeable battery with good cycle performance.


All solid state lithium battery Solid electrolyte Composite electrode Argyrodite type 



The present work was supported by the Japan Science and Technology Agency (JST), Advanced Low Carbon Technology Research and Development Program (ALCA), and Specially Promoted Research for Innovative Next Generation Batteries (SPRING) project. The analysis of SEM was carried out with JIB4600F at the “Joint-use Facilities: Laboratory of Nano-Micro Material Analysis”, Hokkaido University, supported by “Material Analysis and Structure Analysis Open Unit (MASAOU)”.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. 1.
    Sakuda A, Kitaura H, Hayashi A, Tadanaga K, Tatsumisago M (2008) Improvement of high-rate performance of all-solid-state lithium secondary batteries using LiCoO2 coated with Li2O-SiO2 glasses. Electrochem Solid State Lett 11(1):A1–A3. CrossRefGoogle Scholar
  2. 2.
    Auvergniot J, Cassel A, Ledeuil JB, Viallet V, Seznec V, Dedryvere R (2017) Interface stability of argyrodite Li6PS5Cl toward LiCoO2, LiNi1/3Co1/3Mn1/3O2, and LiMn2O4 in bulk all-solid-state batteries. Chem Mater 29(9):3883–3890. CrossRefGoogle Scholar
  3. 3.
    Oh G, Hirayama M, Kwon O, Suzuki K, Kanno R (2016) Bulk-type all solid-state batteries with 5V class LiNi0.5Mn1.5O4 cathode and Li10GeP2S12 solid electrolyte. Chem Mater 28(8):2634–2640. CrossRefGoogle Scholar
  4. 4.
    Zhang Q, Mwizerwa JP, Wan HL, Cai LT, Xu XX, Yao XY (2017) Fe3S4@Li7P3S11 nanocomposites as cathode materials for all-solid-state lithium batteries with improved energy density and low cost. J Mater Chem A 5(45):23919–23925. CrossRefGoogle Scholar
  5. 5.
    Hayashi A, Sakuda A, Tatsumisago M (2016) Development of sulfide solid electrolytes and interface formation processes for bulk-type all-solid-state Li and Na batteries. Front Energy Res 4.
  6. 6.
    Teragawa S, Aso K, Tadanaga K, Hayashi A, Tatsumisago M (2014) Liquid-phase synthesis of a Li3PS4 solid electrolyte using N-methylformamide for all-solid-state lithium batteries. J Mater Chem A 2(14):5095–5099. CrossRefGoogle Scholar
  7. 7.
    Park KH, Oh DY, Choi YE, Nam YJ, Han LL, Kim JY, Xin HL, Lin F, Oh SM, Jung YS (2016) Solution-processable glass LiI-Li4SnS4 superionic conductors for all-solid-state Li-ion batteries. Adv Mater 28(9):1874–1883. CrossRefGoogle Scholar
  8. 8.
    Choi YE, Park KH, Kim DH, Oh DY, Kwak HR, Lee YG, Jung YS (2017) Coatable Li4SnS4 solid electrolytes prepared from aqueous solutions for all-solid-state lithium-ion batteries. Chemsuschem 10(12):2605–2611. CrossRefGoogle Scholar
  9. 9.
    Chida S, Miura A, Rosero-Navarro NC, Higuchi M, Phuc NHH, Muto H, Matsuda A, Tadanaga K (2017) Liquid-phase synthesis of Li6PS5Br using ultrasonication and application to cathode composite electrodes in all-solid-state batteries. Ceram Int 44(1):742. CrossRefGoogle Scholar
  10. 10.
    Yubuchi S, Teragawa S, Aso K, Tadanaga K, Hayashi A, Tatsumisago M (2015) Preparation of high lithium-ion conducting Li6PS5Cl solid electrolyte from ethanol solution for all-solid-state lithium batteries. J Power Sources 293:941–945. CrossRefGoogle Scholar
  11. 11.
    Rosero-Navarro NC, Kinoshita T, Miura A, Higuchi M, Tadanaga K (2017) Effect of the binder content on the electrochemical performance of composite cathode using Li6PS5Cl precursor solution in an all-solid-state lithium battery. Ionics 23(6):1619–1624. CrossRefGoogle Scholar
  12. 12.
    Smith RL (1984) Review of glycol ether and glycol ether ester solvent used in the coating industry. Environ Health Perspect 57:1–4. CrossRefGoogle Scholar
  13. 13.
    Sakuda A, Takeuchi T, Kobayashi H (2016) Electrode morphology in all-solid-state lithium secondary batteries consisting of LiNi1/3Co1/3Mn1/3O2 and Li2S-P2S5 solid electrolytes. Solid State Ion 285:112–117. CrossRefGoogle Scholar
  14. 14.
    Ohta N, Takada K, Sakaguchi I, Zhang LQ, Ma RZ, Fukuda K, Osada M, Sasaki T (2007) LiNbO3-coated LiCoO2 as cathode material for all solid-state lithium secondary batteries. Electrochem Commun 9(7):1486–1490. CrossRefGoogle Scholar
  15. 15.
    Calpa M, Rosero-Navarro NC, Miura A, Tadanaga K (2017) Instantaneous preparation of high lithium-ion conducting sulfide solid electrolyte Li7P3S11 by a liquid phase process. RSC Adv 7(73):46499–46504. CrossRefGoogle Scholar
  16. 16.
    Deiseroth HJ, Kong ST, Eckert H, Vannahme J, Reiner C, Zaiß T, Schlosser M (2008) Li6PS5X: a class of crystalline Li-rich solids with an unusually high Li+ mobility. Angew Chem, Int Ed 47(4):755–758. CrossRefGoogle Scholar
  17. 17.
    Yu C, van Eijck L, Ganapathy S, Wagemaker M (2016) Synthesis, structure and electrochemical performance of the argyrodite Li6PS5Cl solid electrolyte for Li-ion solid state batteries. Electrochim Acta 215:93–99. CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • Nataly Carolina Rosero-Navarro
    • 1
  • Akira Miura
    • 1
  • Kiyoharu Tadanaga
    • 1
    Email author
  1. 1.Division of Applied Chemistry, Faculty of EngineeringHokkaido UniversitySapporoJapan

Personalised recommendations