Batteries are a key technology in modern society1,2. They are used to power electric and hybrid electric vehicles and to store wind and solar energy in smart grids. Electrochemical devices with high energy and power densities can currently be powered only by batteries with organic liquid electrolytes. However, such batteries require relatively stringent safety precautions, making large-scale systems very complicated and expensive. The application of solid electrolytes is currently limited because they attain practically useful conductivities (10−2 S cm−1) only at 50–80 °C, which is one order of magnitude lower than those of organic liquid electrolytes3,4,5,6,7,8. Here, we report a lithium superionic conductor, Li10GeP2S12 that has a new three-dimensional framework structure. It exhibits an extremely high lithium ionic conductivity of 12 mS cm−1 at room temperature. This represents the highest conductivity achieved in a solid electrolyte, exceeding even those of liquid organic electrolytes. This new solid-state battery electrolyte has many advantages in terms of device fabrication (facile shaping, patterning and integration), stability (non-volatile), safety (non-explosive) and excellent electrochemical properties (high conductivity and wide potential window)9,10,11.
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Tarascon, J. M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).
Armand, M. & Tarascon, J. M. Building better batteries. Nature 451, 652–657 (2008).
Inaguma, Y. et al. High ionic-conductivity in lithium lanthanum titanate. Solid State Commun. 86, 689–693 (1993).
Kanno, R. & Maruyama, M. Lithium ionic conductor thio-LISICON—the Li2S–GeS2–P2S5 system. J. Electrochem. Soc. 148, A742–A746 (2001).
Mizuno, F., Hayashi, A., Tadanaga, K. & Tatsumisago, M. New, highly ion-conductive crystals precipitated from Li2S–P2S5 glasses. Adv. Mater. 17, 918–921 (2005).
Hayashi, A., Minami, K., Mizuno, F. & Tatsumisago, M. Formation of Li+ superionic crystals from the Li2S–P2S5 melt-quenched glasses. J. Mater. Sci. 43, 1885–1889 (2008).
Kondo, S., Takada, K. & Yamamura, Y. New lithium ion conductors based on Li2S–SiS2 system. Solid State Ion. 53, 1183–1186 (1992).
Takada, K., Aotani, N. & Kondo, S. Electrochemical behaviors of Li+ ion conductor, Li3PO4–Li2S–SiS2 . J. Power Sources 43, 135–141 (1993).
Inada, T. et al. All solid-state sheet battery using lithium inorganic solid electrolyte, thio-LISICON. J. Power Sources 194, 1085–1088 (2009).
Kobayashi, T. et al. All solid-state battery with sulfur electrode and thio-LISICON electrolyte. J. Power Sources 182, 621–625 (2008).
Kobayashi, T., Yamada, A. & Kanno, R. Interfacial reactions at electrode/electrolyte boundary in all solid-state lithium battery using inorganic solid electrolyte, thio-LISICON. Electrochim. Acta 53, 5045–5050 (2008).
Alpen, U. V., Rabenau, A. & Talat, G. H. Ionic-conductivity in Li3N single-crystals. Appl. Phys. Lett. 30, 621–623 (1977).
Lapp, T., Skaarup, S. & Hooper, A. Ionic-conductivity of pure and doped Li3N. Solid State Ion. 11, 97–103 (1983).
Edman, L., Ferry, A. & Doeff, M. M. Slow recrystallization in the polymer electrolyte system poly(ethylene oxide)(n)-LiN(CF3SO2)(2). J. Mater. Res. 15, 1950–1954 (2000).
Croce, F., Appetecchi, G. B., Persi, L. & Scrosati, B. Nanocomposite polymer electrolytes for lithium batteries. Nature 394, 456–458 (1998).
Stallworth, P. E. et al. NMR, DSC and high pressure electrical conductivity studies of liquid and hybrid electrolytes. J. Power Sources 81, 739–747 (1999).
Rabenau, A. Lithium nitride and related materials—case-study of the use of modern solid-state research techniques. Solid State Ion. 6, 277–293 (1982).
Garcia-Martin, S., Rojo, J. M., Tsukamoto, H., Moran, E. & Alario-Franco, M. A. Lithium-ion conductivity in the novel La1/3−xLi3xNbO3 solid solution with perovskite-related structure. Solid State Ion. 116, 11–18 (1999).
Neudecker, B. J. & Weppner, W. Li9SiAlO8: A lithium ion electrolyte for voltages above 5.4 V. J. Electrochem. Soc. 143, 2198–2203 (1996).
Song, J. Y., Wang, Y. Y. & Wan, C. C. Conductivity study of porous plasticized polymer electrolytes based on poly(vinylidene fluoride)—A comparison with polypropylene separators. J. Electrochem. Soc. 147, 3219–3225 (2000).
Saruwatari, H., Kuboki, T., Kishi, T., Mikoshiba, S. & Takami, N. Imidazolium ionic liquids containing LiBOB electrolyte for lithium battery. J. Power Sources 195, 1495–1499 (2010).
Boultif, A. & Louer, D. Indexing of powder diffraction patterns for low-symmetry lattice by the successive dichotomy method. J. Appl. Crystallogr. 24, 987–993 (1991).
Favre-Nicolin, V. & Cerny, R. FOX, ‘free objects for crystallography’: A modular approach to ab initio structure determination from powder diffraction. J. Appl. Crystallogr. 35, 734–743 (2002).
Izumi, F. & Momma, K. Three-dimensional visualization in powder diffraction. Solid State Phenom. 130, 15–20 (2007).
Oishi, R. et al. Rietveld analysis software for J-PARC. Nucl. Instrum. Methods Phys. Res. 600, 94–96 (2009).
Ohta, N. et al. LiNbO3-coated LiCoO2 as cathode material for all solid-state lithium secondary batteries. Electrochem. Commun. 9, 1486–1490 (2007).
This work was partially supported by a Grant-in-Aid for Scientific Research (A) from the Japan Society for the Promotion of Science. The synchrotron and neutron radiation experiments were carried out as projects approved by the Japan Synchrotron Radiation Research Institute (JASRI) (proposal No 2010A1584) and the Japan Proton Accelerator Research Complex (J-PARC) and Institute of Materials Structure Science (proposal No 2009B0039 and No. 2010A0060), respectively.
The authors declare no competing financial interests.
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Kamaya, N., Homma, K., Yamakawa, Y. et al. A lithium superionic conductor. Nature Mater 10, 682–686 (2011). https://doi.org/10.1038/nmat3066