High-power all-solid-state batteries using sulfide superionic conductors


Compared with lithium-ion batteries with liquid electrolytes, all-solid-state batteries offer an attractive option owing to their potential in improving the safety and achieving both high power and high energy densities. Despite extensive research efforts, the development of all-solid-state batteries still falls short of expectation largely because of the lack of suitable candidate materials for the electrolyte required for practical applications. Here we report lithium superionic conductors with an exceptionally high conductivity (25 mS cm−1 for Li9.54Si1.74P1.44S11.7Cl0.3), as well as high stability ( 0 V versus Li metal for Li9.6P3S12). A fabricated all-solid-state cell based on this lithium conductor is found to have very small internal resistance, especially at 100 C. The cell possesses high specific power that is superior to that of conventional cells with liquid electrolytes. Stable cycling with a high current density of 18 C (charging/discharging in just three minutes; where C is the C-rate) is also demonstrated.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Figure 1: X-ray diffraction patterns of the LGPS family.
Figure 2: Ionic conductivity and crystal structure of Li9.54Si1.74P1.44S11.7Cl0.3.
Figure 3: Electrochemical stability of the LGPS family.
Figure 4: Performance of the all-solid-state cells.
Figure 5: Chronoamperometric behaviours of the all-solid-state and lithium-ion cells.
Figure 6: The Ragone plot.


  1. 1

    Armand, M. & Tarascon, J. M. Building better batteries. Nature 451, 652–657 (2008).

    Google Scholar 

  2. 2

    Simon, P. & Gogotsi, Y. Materials for electrochemical capacitors. Nature Mater. 7, 845–854 (2008).

    Article  Google Scholar 

  3. 3

    Scrosati, B. & Garche, J. Lithium batteries: status, prospects and future. J. Power Sources 195, 2419–2430 (2010).

    Article  Google Scholar 

  4. 4

    Goodenough, J. Rechargeable batteries: challenges old and new. J. Solid State Electrochem. 16, 2019–2029 (2012).

    Article  Google Scholar 

  5. 5

    Winter, M. & Brodd, R. J. What are batteries, fuel cells, and supercapacitors? Chem. Rev. 104, 4245–4269 (2004).

    Article  Google Scholar 

  6. 6

    Robinson, A. L. & Janek, J. Solid-state batteries enter EV fray. MRS Bull. 39, 1046–1047 (2014).

    Article  Google Scholar 

  7. 7

    Seino, Y. et al. A sulphide lithium super ion conductor is superior to liquid ion conductors for use in rechargeable batteries. Energy Environ. Sci. 7, 627–631 (2014).

    Article  Google Scholar 

  8. 8

    Kamaya, N. et al. A lithium superionic conductor. Nature Mater. 10, 682–686 (2011).

    Article  Google Scholar 

  9. 9

    Wang, Y. et al. Design principles for solid-state lithium superionic conductors. Nature Mater. 14, 1026-1031 (2015).

    Google Scholar 

  10. 10

    Ohtomo, T. et al. All-solid-state lithium secondary batteries using the 75Li2S25P2S5 glass and the 70Li2S30P2S5 glass-ceramic as solid electrolytes. J. Power Sources 233, 231–235 (2013).

    Article  Google Scholar 

  11. 11

    Kwon, O. et al. Synthesis, structure, and conduction mechanism of the lithium superionic conductor Li10+δGe1+δP2−δS12 . J. Mater. Chem. A 3, 438–446 (2015).

    Article  Google Scholar 

  12. 12

    Hori, S. et al. Structure–property relationships in lithium superionic conductors having a Li10GeP2S12-type structure. Acta Crystallogr. B B71, 727–736 (2015).

    Article  Google Scholar 

  13. 13

    Kanno, R. et al. A self-assembled breathing interface for all-solid-state ceramic lithium batteries. Electrochem. Solid-State Lett. 7, A455-A458 (2004).

    Article  Google Scholar 

  14. 14

    Bron, P. et al. Li10SnP2S12: an affordable lithium superionic conductor. J. Am. Chem. Soc. 135, 15694–15697 (2013).

    Article  Google Scholar 

  15. 15

    Kuhn, A. et al. A new ultrafast superionic Li-conductor: ion dynamics in Li11Si2PS12 and comparison with other tetragonal LGPS-type electrolytes. Phys. Chem. Chem. Phys. 16, 14669–14674 (2014).

    Article  Google Scholar 

  16. 16

    Hori, S. et al. Synthesis, structure, and ionic conductivity of solid solution, Li10+δ M1+δP2−δS12 (M = Si, Sn). Faraday Discuss. 176, 83–94 (2014).

    Article  Google Scholar 

  17. 17

    Huang, W. & Frech, R. Vibrational spectroscopic and electrochemical studies of the low and high temperature phases of LiCo1−xMxO2 (M = Ni or Ti). Solid State Ion. 86–88, 395–400 (1996).

    Article  Google Scholar 

  18. 18

    Ohta, S., Kobayashi, T., Seki, J. & Asaoka, T. Electrochemical performance of an all-solid-state lithium ion battery with garnet-type oxide electrolyte. J. Power Sources 202, 332–335 (2012).

    Article  Google Scholar 

  19. 19

    Aoki, K., Baars, A., Jaworski, A. & Osteryoung, J. Chronoamperometry of strong acids without supporting electrolyte. J. Electroanal. Chem. 472, 1–6 (1999).

    Article  Google Scholar 

  20. 20

    Wetjen, M., Kim, G.-T., Joost, M., Winter, M. & Passerini, S. Temperature dependence of electrochemical properties of cross-linked poly(ethylene oxide)–lithium bis(trifluoromethanesulfonyl)imide–N-butyl-N-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide solid polymer electrolytes for lithium batteries. Electrochim. Acta 87, 779–787 (2013).

    Article  Google Scholar 

  21. 21

    Capiglia, C. et al. 7Li and 19F diffusion coefficients and thermal properties of non-aqueous electrolyte solutions for rechargeable lithium batteries. J. Power Sources 81–82, 859–862 (1999).

    Article  Google Scholar 

  22. 22

    Abe, T., Fukuda, H., Iriyama, Y. & Ogumi, Z. Solvated Li-ion transfer at interface between graphite and electrolyte. J. Electrochem. Soc. 151, A1120–A1123 (2004).

    Article  Google Scholar 

  23. 23

    Abe, T., Sagane, F., Ohtsuka, M., Iriyama, Y. & Ogumi, Z. Lithium-ion transfer at the interface between lithium-ion conductive ceramic electrolyte and liquid electrolyte—A key to enhancing the rate capability of lithium-ion batteries. J. Electrochem. Soc. 152, A2151–A2154 (2005).

    Article  Google Scholar 

  24. 24

    Choi, D. et al. Li-ion batteries from LiFePO4 cathode and anatase/graphene composite anode for stationary energy storage. Electrochem. Commun. 12, 378–381 (2010).

    Article  Google Scholar 

  25. 25

    Lee, S. W. et al. High-power lithium batteries from functionalized carbon-nanotube electrodes. Nature Nanotech. 5, 531–537 (2010).

    Article  Google Scholar 

  26. 26

    Nagasubramanian, G. Electrical characteristics of 18650 Li-ion cells at low temperatures. J. Appl. Electrochem. 31, 99–104 (2001).

    Article  Google Scholar 

  27. 27

    Cericola, D., Novák, P., Wokaun, A. & Köttz, R. Hybridization of electrochemical capacitors and rechargeable batteries: an experimental analysis of the different possible approaches utilizing activated carbon, Li4Ti5O12 and LiMn2O4 . J. Power Sources 196, 10305–10313 (2011).

    Article  Google Scholar 

  28. 28

    Khomenko, V., Raymundo-Piñero, E. & Béguin, F. A new type of high energy asymmetric capacitor with nanoporous carbon electrodes in aqueous electrolyte. J. Power Sources 195, 4234–4241 (2010).

    Article  Google Scholar 

  29. 29

    Zhang, J., Jiang, J., Li, H. & Zhao, X. S. A high-performance asymmetric supercapacitor fabricated with graphene-based electrodes. Energy Environ. Sci. 4, 4009–4015 (2011).

    Article  Google Scholar 

  30. 30

    Gallant, B. M. et al. The Lithium Air Battery 121–158 (Springer, 2014).

    Google Scholar 

  31. 31

    Peng, H.-J. et al. Nanoarchitectured graphene/CNT@porous carbon with extraordinary electrical conductivity and interconnected micro/mesopores for lithium-sulfur batteries. Adv. Funct. Mater. 24, 2772–2781 (2014).

    Article  Google Scholar 

  32. 32

    Imamura, D., Miyama, M., Hibino, M. & Kubo, T. Mg intercalation properties into V2O5 gel/carbon composites under high-rate condition. J. Electrochem. Soc. 150, A753–A758 (2003).

    Article  Google Scholar 

  33. 33

    Lin, M.-C. et al. An ultrafast rechargeable aluminium-ion battery. Nature 520, 324–328 (2015).

    Article  Google Scholar 

  34. 34

    Li, S. et al. Effect of carbon matrix dimensions on the electrochemical properties of Na3V2(PO4)3 nanograins for high-performance symmetric sodium-ion batteries. Adv. Mater. 26, 3545–3553 (2014).

    Article  Google Scholar 

  35. 35

    Ohta, N. et al. Enhancement of the high-rate capability of solid-state lithium batteries by nanoscale interfacial modification. Adv. Mater. 18, 2226–2229 (2006).

    Article  Google Scholar 

  36. 36

    Maier, J. Nanoionics: ion transport and electrochemical storage in confined systems. Nature Mater. 4, 806–815 (2005).

    Article  Google Scholar 

  37. 37

    Oishi, R. et al. Rietveld analysis software for J-PARC. Nucl. Instrum. Methods Phys. Res. A 600, 94–96 (2009).

    Article  Google Scholar 

  38. 38

    Ishikawa, Y. et al. Z-MEM & Z-3D, maximum entropy method and visualization software for electron/nuclear density distribution in Z-Code. In ICANS XXI DAA-P08 (J-PARC, 2014).

  39. 39

    Sakata, M. & Sato, M. Accurate structure analysis by the maximum-entropy method. Acta Crystallogr. A 46, 263–270 (1990).

    Article  Google Scholar 

  40. 40

    Ishikawa, Y., Yonemura, M. & Kamiyama, T. Z-3D, Textbook of Z-code Powder Diffraction Data Analysis School (KEK, 2014).

    Google Scholar 

  41. 41

    Ohta, N. et al. LiNbO3-coated LiCoO2 as cathode material for all solid-state lithium secondary batteries. Electrochem. Commun. 9, 1486–1490 (2007).

    Article  Google Scholar 

Download references


The authors thank T. Yabutani, R. Saito and K. Mukoyama for their support in the preparation of the all-solid-state and lithium-ion cells. They also thank H. Hirokawa for his support in the synthesis of Li9.6P3S12. This study was supported by the Post-LiEAD project of the New Energy and Industry Technology Development Organization (NEDO), Japan. The synchrotron radiation experiments were carried out as projects approved by the Japan Synchrotron Radiation Institute (JASRI) (proposal No. 2014A1408 and 2014A1763). The neutron radiation experiments were performed at the Japan Proton Accelerator Research Complex (J-PARC) (proposal No. 2014AM1004, 2014BM0006 and 2014BM0012).

Author information




Y.K. and S.H. designed and conducted the experimental work. Y.K., S.H., T.S., K.S., M.H. and R.K. analysed the electrochemical data. S.H., A.M. and M.Y. measured the synchrotron X-ray and neutron diffraction of superionic conductors. Y.K., S.H., M.Y. and R.K. analysed the crystal structure. Y.K., S.H. and R.K. wrote the manuscript. H.I. and R.K. directed this work.

Corresponding authors

Correspondence to Yuki Kato or Ryoji Kanno.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Figures 1–12, Supplementary Table 1–6, Supplementary Methods and Supplementary References. (PDF 2379 kb)

Supplementary Video 1

Description of the bi-polar stacking cell system. (MP4 47865 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Kato, Y., Hori, S., Saito, T. et al. High-power all-solid-state batteries using sulfide superionic conductors. Nat Energy 1, 16030 (2016). https://doi.org/10.1038/nenergy.2016.30

Download citation

Further reading


Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing