Design principles for solid-state lithium superionic conductors

Journal name:
Nature Materials
Year published:
Published online


Lithium solid electrolytes can potentially address two key limitations of the organic electrolytes used in today’s lithium-ion batteries, namely, their flammability and limited electrochemical stability. However, achieving a Li+ conductivity in the solid state comparable to existing liquid electrolytes (>1mScm−1) is particularly challenging. In this work, we reveal a fundamental relationship between anion packing and ionic transport in fast Li-conducting materials and expose the desirable structural attributes of good Li-ion conductors. We find that an underlying body-centred cubic-like anion framework, which allows direct Li hops between adjacent tetrahedral sites, is most desirable for achieving high ionic conductivity, and that indeed this anion arrangement is present in several known fast Li-conducting materials and other fast ion conductors. These findings provide important insight towards the understanding of ionic transport in Li-ion conductors and serve as design principles for future discovery and design of improved electrolytes for Li-ion batteries.

At a glance


  1. Mapping of the anion sublattice to a bcc/fcc/hcp framework in solid-state Li-ion conductors.
    Figure 1: Mapping of the anion sublattice to a bcc/fcc/hcp framework in solid-state Li-ion conductors.

    ae, Crystal structure of Li-ion conductors Li10GeP2S12 (a), Li7P3S11 (b), Li2S (c), γ-Li3PS4 (d) and Li4GeS4 (e). Li atom, partially occupied Li atom, S atom, PS4 tetrahedra and GeS4 tetrahedra (partially occupied in Li10GeP2S12) are coloured green, green–white, yellow, purple and blue, respectively. In both Li10GeP2S12 and Li7P3S11, the sulphur anion sublattice can be closely mapped to a bcc framework (red circles connected by red lines). In Li2S, the anion sublattice is an exact fcc matrix (yellow–red circles). The anion sublattices in γ-Li3PS4 and Li4GeS4 are closely matched to a hcp framework.

  2. Li-ion migration pathways in bcc/fcc/hcp-type anion lattices.
    Figure 2: Li-ion migration pathways in bcc/fcc/hcp-type anion lattices.

    ac, Li-ion migration path (left panels) and calculated energy path (right panels) in bcc (a), fcc (b) and hcp (c) sulphur lattices. The sulphur anions are coloured yellow, and the Li ions are coloured green, blue and red for different paths. LiS4 tetrahedra and LiS6 octahedra are coloured green and red, respectively.

  3. Activation barrier for Li-ion migration versus lattice volume.
    Figure 3: Activation barrier for Li-ion migration versus lattice volume.

    Activation barrier calculated for the Li-ion migration pathways in the bcc/fcc/hcp S2− lattices at different volumes. Solid and dotted lines are guides to the eye. Experimental activation energies for Li10GeP2S12 (ref. 15), Li10SnP2S12 (refs 17,18), Li10SiP2S12 (ref. 19), Li7P3S11 (ref. 13), Li2S (ref. 42), Li4GeS4 (ref. 26) and γ-Li3PS4 (ref. 26) are marked by a star symbol for comparison. The underestimate of the activation energy for Li2S is due to fact that the experimental value contains contributions from the defect formation energy.

  4. Li-ion probability densities in Li-ion conductors.
    Figure 4: Li-ion probability densities in Li-ion conductors.

    ad, The probability densities of Li ions are obtained from ab initio molecular dynamics simulations at 900K in Li10GeP2S12 (a), Li7P3S11 (b), Li2S (c) and Li4GeS4 (d). Isosurfaces of the ionic probability densities are plotted at increasing isovalues ranging from 2P0 to 32P0, in which P0 is defined as the mean value of the density for each structure. PS4 tetrahedra and GeS4 tetrahedra are coloured purple and blue, respectively. The sulphur atoms are shown as small yellow circles for Li2S.

  5. Similarity of screened ICSD structures containing Li and S to a bcc anion framework using the structural matching algorithm.
    Figure 5: Similarity of screened ICSD structures containing Li and S to a bcc anion framework using the structural matching algorithm.

    Compounds with transition-metal cations are excluded. The lattice length deviation is defined as σl = 1 − min(a, b, c)/max(a, b, c), and the angle deviation is defined as σθ = max(|90° − α|, |90° − β|, |90° − γ|), where a, b, c, α, β and γ are the conventional unit-cell parameters of the transformed lattice (see Methods and Supplementary Fig. 1). For an ideal compound with a perfect bcc anion framework σl = σθ = 0.


  1. Gallagher, S. Boeing’s Dreamliner batteries ‘inherently unsafe’—and yours may be too. Ars Technica (January, 2013);
  2. Meier, F. & Woodyard, C. Feds review third Tesla fire as shares fall again. USA Today (7 November 2013);
  3. Knauth, P. Inorganic solid Li ion conductors: An overview. Solid State Ion. 180, 911916 (2009).
  4. Bates, J. B., Dudney, N. J., Neudecker, B., Ueda, A. & Evans, C. D. Thin-film lithium and lithium-ion batteries. Solid State Ion. 135, 3345 (2000).
  5. Li, J., Ma, C., Chi, M., Liang, C. & Dudney, N. J. Solid electrolyte: The key for high-voltage lithium batteries. Adv. Energy Mater. 5, 1401408 (2015).
  6. Bruce, P. G. The A-C conductivity of polycrystalline LISICON, Li2+2xZn1−xGeO4, and a model for intergranular constriction resistances. J. Electrochem. Soc. 130, 662669 (1983).
  7. Aono, H. Ionic conductivity of solid electrolytes based on lithium titanium phosphate. J. Electrochem. Soc. 137, 10231027 (1990).
  8. Inaguma, Y. et al. High ionic conductivity in lithium lanthanum titanate. Solid State Commun. 86, 689693 (1993).
  9. Murugan, R., Thangadurai, V. & Weppner, W. Fast lithium ion conduction in garnet-type Li7La3Zr2O12. Angew. Chem. Int. Ed. 46, 77787781 (2007).
  10. Yu, X., Bates, J. B., Jellison, G. E. Jr & Hart, F. X. A stable thin-film lithium electrolyte: Lithium phosphorus oxynitride. J. Electrochem. Soc. 144, 524532 (1997).
  11. Kanno, R. & Murayama, M. Lithium ionic conductor thio-LISICON: The Li2S–GeS2–P2S5 system. J. Electrochem. Soc. 148, A742 (2001).
  12. Yamane, H. et al. Crystal structure of a superionic conductor, Li7P3S11. Solid State Ion. 178, 11631167 (2007).
  13. Seino, Y., Ota, T., Takada, K., Hayashi, A. & Tatsumisago, M. A sulphide lithium super ion conductor is superior to liquid ion conductors for use in rechargeable batteries. Energy Environ. Sci. 7, 627631 (2014).
  14. Kamaya, N. et al. A lithium superionic conductor. Nature Mater. 10, 682686 (2011).
  15. Kuhn, A., Duppel, V. & Lotsch, B. V. Tetragonal Li10GeP2S12 and Li7GePS8—exploring the Li ion dynamics in LGPS Li electrolytes. Energy Environ. Sci. 6, 35483552 (2013).
  16. Ong, S. P. et al. Phase stability, electrochemical stability and ionic conductivity of the Li10 ± 1MP2X12 (M = Ge, Si, Sn, Al or P, and X = O, S or Se) family of superionic conductors. Energy Environ. Sci. 6, 148156 (2013).
  17. Bron, P. et al. Li10SnP2S12: An affordable lithium superionic conductor. J. Am. Chem. Soc. 135, 1569415697 (2013).
  18. 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, 1466914674 (2014).
  19. Whiteley, J. M., Woo, J. H., Hu, E., Nam, K.-W. & Lee, S.-H. Empowering the lithium metal battery through a silicon-based superionic conductor. J. Electrochem. Soc. 161, A1812A1817 (2014).
  20. Kato, Y. et al. Synthesis, structure and lithium ionic conductivity of solid solutions of Li10(Ge1−xMx)P2S12 (M = Si, Sn). J. Power Sources 271, 6064 (2014).
  21. Van der Ven, A., Bhattacharya, J. & Belak, A. A. Understanding Li diffusion in Li-intercalation compounds. Acc. Chem. Res. 46, 12161225 (2013).
  22. Urban, A., Lee, J. & Ceder, G. The configurational space of rocksalt-type oxides for high-capacity lithium battery electrodes. Adv. Energy Mater. 4, 1400478 (2014).
  23. Kuhn, A., Köhler, J. & Lotsch, B. V. Single-crystal X-ray structure analysis of the superionic conductor Li10GeP2S12. Phys. Chem. Chem. Phys. 15, 1162011622 (2013).
  24. Kang, K. & Ceder, G. Factors that affect Li mobility in layered lithium transition metal oxides. Phys. Rev. B 74, 094105 (2006).
  25. Inorganic Crystal Structure Database (FIZ Karlsruhe, 2014);
  26. Murayama, M., Sonoyama, N., Yamada, A. & Kanno, R. Material design of new lithium ionic conductor, thio-LISICON, in the Li2S–P2S5 system. Solid State Ion. 170, 173180 (2004).
  27. Van der Ven, A., Ceder, G., Asta, M. & Tepesch, P. First-principles theory of ionic diffusion with nondilute carriers. Phys. Rev. B 64, 184307 (2001).
  28. Mo, Y., Ong, S. P. & Ceder, G. First principles study of the Li10GeP2S12 lithium super ionic conductor material. Chem. Mater. 24, 1517 (2012).
  29. Vinatier, P., Gravereau, P., Ménétrier, M., Trut, L. & Levasseur, A. Li3BS3. Acta Crystallogr. C 50, 11801183 (1994).
  30. Homma, K. et al. Crystal structure and phase transitions of the lithium ionic conductor Li3PS4. Solid State Ion. 182, 5358 (2011).
  31. Liu, Z. et al. Anomalous high ionic conductivity of nanoporous β-Li3PS4. J. Am. Chem. Soc. 135, 2023 (2013).
  32. Zhao, Y. & Daemen, L. L. Superionic conductivity in lithium-rich anti-perovskites. J. Am. Chem. Soc. 134, 1504215047 (2012).
  33. Emly, A., Kioupakis, E. & Van der Ven, A. Phase stability and transport mechanisms in antiperovskite Li3OCl and Li3OBr superionic conductors. Chem. Mater. 25, 46634670 (2013).
  34. Hull, S. Superionics: Crystal structures and conduction processes. Rep. Prog. Phys. 67, 12331314 (2004).
  35. Yoo, H. D. et al. Mg rechargeable batteries: An on-going challenge. Energy Environ. Sci. 6, 22652279 (2013).
  36. Deiseroth, H. J. et al. Li6PS5X: A class of crystalline Li-rich solids with an unusually high Li+ mobility. Angew. Chem. Int. Ed. 47, 755758 (2008).
  37. Hayashi, A., Noi, K., Sakuda, A. & Tatsumisago, M. Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries. Nature Commun. 3, 856 (2012).
  38. Tanibata, N. et al. X-ray crystal structure analysis of sodium-ion conductivity in 94Na3PS4 ⋅ 6Na4SiS4 glass-ceramic electrolytes. ChemElectroChem 1, 11301132 (2014).
  39. Xie, H., Alonso, J. A., Li, Y., Fernández-Díaz, M. T. & Goodenough, J. B. Lithium distribution in aluminum-free cubic Li7La3Zr2O12. Chem. Mater. 23, 35873589 (2011).
  40. Xu, M. et al. Mechanisms of Li+ transport in garnet-type cubic Li3+xLa3M2O12 (M = Te, Nb, Zr). Phys. Rev. B 85, 052301 (2012).
  41. Miara, L. J. et al. Effect of Rb and Ta doping on the ionic conductivity and stability of the garnet Li7+2xy (La3−xRbx) (Zr2−yTay)O12 (0 ≤ x ≤ 0.375,0 ≤ y ≤ 1) superionic conductor: A first principles investigation. Chem. Mater. 25, 30483055 (2013).
  42. Lin, Z., Liu, Z., Dudney, N. J. & Liang, C. Lithium superionic sulfide cathode for all-solid lithium–sulfur batteries. ACS Nano 7, 28292833 (2013).
  43. Ong, S. P. et al. Python materials genomics (pymatgen): A robust, open-source python library for materials analysis. Comput. Mater. Sci. 68, 314319 (2013).
  44. Momma, K. & Izumi, F. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 12721276 (2011).
  45. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 38653868 (1996).
  46. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 1795317979 (1994).
  47. Kresse, G. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 1116911186 (1996).
  48. Henkelman, G., Uberuaga, B. P. & Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 99019904 (2000).

Download references

Author information


  1. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

    • Yan Wang,
    • William Davidson Richards,
    • Shyue Ping Ong,
    • Jae Chul Kim,
    • Yifei Mo &
    • Gerbrand Ceder
  2. Department of NanoEngineering, University of California, San Diego, La Jolla, California 92093, USA

    • Shyue Ping Ong
  3. Samsung Advanced Institute of Technology-USA, 1 Cambridge Center, Suite 702, Cambridge, Massachusetts 02142, USA

    • Lincoln J. Miara
  4. Department of Materials Science and Engineering, University of Maryland, College Park Maryland 20742, USA

    • Yifei Mo
  5. Department of Materials Science and Engineering, University of California, Berkeley, California 94720, USA

    • Gerbrand Ceder
  6. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

    • Gerbrand Ceder


G.C., W.D.R. and Y.W. proposed the concept. Y.W. carried out the calculations and together with W.D.R. prepared the manuscript initially. W.D.R. conceived and implemented the structural matcher algorithm. All authors contributed to the discussions and revisions of the manuscript.

Competing financial interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to:

Author details

Supplementary information

PDF files

  1. Supplementary Information (2,530 KB)

    Supplementary Information

Additional data