Abstract
Superionic lithium conductivity has only been discovered in a few classes of materials, mostly found in thiophosphates and rarely in oxides. Herein, we reveal that corner-sharing connectivity of the oxide crystal structure framework promotes superionic conductivity, which we rationalize from the distorted lithium environment and reduced interaction between lithium and non-lithium cations. By performing a high-throughput search for materials with this feature, we discover ten new oxide frameworks predicted to exhibit superionic conductivity—from which we experimentally demonstrate LiGa(SeO3)2 with a bulk ionic conductivity of 0.11 mS cm−1 and an activation energy of 0.17 eV. Our findings provide insight into the factors that govern fast lithium mobility in oxide materials and will accelerate the development of new oxide electrolytes for all-solid-state batteries.
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Data availability
All relevant data within the article are available from the corresponding author upon reasonable request. Source data are provided with this paper and within the Supplementary Information.
Code availability
A sample code to perform our analysis on the geometry of tetrahedral/octahedral environment is provided in the Supplementary Information.
References
Schmuch, R., Wagner, R., Hörpel, G., Placke, T. & Winter, M. Performance and cost of materials for lithium-based rechargeable automotive batteries. Nat. Energy 3, 267–278 (2018).
Randau, S. et al. Benchmarking the performance of all-solid-state lithium batteries. Nat. Energy https://doi.org/10.1038/s41560-020-0565-1 (2020).
Famprikis, T., Canepa, P., Dawson, J. A., Islam, M. S. & Masquelier, C. Fundamentals of inorganic solid-state electrolytes for batteries. Nat. Mater. https://doi.org/10.1038/s41563-019-0431-3 (2019).
Nam, Y. J., Oh, D. Y., Jung, S. H. & Jung, Y. S. Toward practical all-solid-state lithium-ion batteries with high energy density and safety: comparative study for electrodes fabricated by dry- and slurry-mixing processes. J. Power Sources 375, 93–101 (2018).
Barroso-Luque, L., Tu, Q. & Ceder, G. An analysis of solid-state electrodeposition-induced metal plastic flow and predictions of stress states in solid ionic conductor defects. J. Electrochem. Soc. 167, 020534 (2020).
Kamaya, N. et al. A lithium superionic conductor. Nat. Mater. 10, 682–686 (2011).
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, 627–631 (2014).
Zhou, L., Assoud, A., Zhang, Q., Wu, X. & Nazar, L. F. New family of argyrodite thioantimonate lithium superionic conductors. J. Am. Chem. Soc. 141, 19002–19013 (2019).
Yamane, H. et al. Crystal structure of a superionic conductor, Li7P3S11. Solid State Ion. 178, 1163–1167 (2007).
Richards, W. D., Miara, L. J., Wang, Y., Kim, J. C. & Ceder, G. Interface stability in solid-state batteries. Chem. Mater. 28, 266–273 (2016).
Xiao, Y. et al. Understanding interface stability in solid-state batteries. Nat. Rev. Mater. https://doi.org/10.1038/s41578-019-0157-5 (2019).
Wood, K. N. et al. Operando X-ray photoelectron spectroscopy of solid electrolyte interphase formation and evolution in Li2S-P2S5 solid-state electrolytes. Nat. Commun. 9, 2490 (2018).
Wenzel, S. et al. Direct observation of the interfacial instability of the fast ionic conductor Li10GeP2S12 at the lithium metal anode. Chem. Mater. 28, 2400–2407 (2016).
Lian, P.-J. et al. Inorganic sulfide solid electrolytes for all-solid-state lithium secondary batteries. J. Mater. Chem. A 7, 20540–20557 (2019).
Xu, X. et al. Li7P3S11 solid electrolyte coating silicon for high-performance lithium-ion batteries. Electrochim. Acta 276, 325–332 (2018).
Zhang, Z. et al. New horizons for inorganic solid state ion conductors. Energy Environ. Sci. 11, 1945–1976 (2018).
Aono, H. Ionic conductivity of solid electrolytes based on lithium titanium phosphate. J. Electrochem. Soc. 137, 1023 (1990).
Murugan, R., Thangadurai, V. & Weppner, W. Fast lithium ion conduction in garnet‐type Li7La3Zr2O12. Angew. Chem. Int. Ed. 46, 7778–7781 (2007).
Stramare, S., Thangadurai, V. & Weppner, W. Lithium lanthanum titanates: a review. Chem. Mater. 15, 3974–3990 (2003).
Wang, Y. et al. Design principles for solid-state lithium superionic conductors. Nat. Mater. 14, 1026–1031 (2015).
Richards, W. D., Wang, Y., Miara, L. J., Kim, J. C. & Ceder, G. Design of Li1+2x Zn1−x PS4, a new lithium ion conductor. Energ. Environ. Sci. 9, 3272–3278 (2016).
Suzuki, N. et al. Synthesis and electrochemical properties of I¯4 type Li1+2xZn1-xPS4 solid electrolyte. Chem. Mater. https://doi.org/10.1021/acs.chemmater.7b03833 (2018).
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. Energ. Environ. Sci. 6, 148–156 (2012).
Kanno, R., Hata, T., Kawamoto, Y. & Irie, M. Synthesis of a new lithium ionic conductor, thio-LISICON–lithium germanium sulfide system. Solid State Ion. 130, 97–104 (2000).
Knauth, P. Inorganic solid Li ion conductors: an overview. Solid State Ion. 180, 911–916 (2009).
Sendek, A. D. et al. Holistic computational structure screening of more than 12000 candidates for solid lithium-ion conductor materials. Energ. Environ. Sci. 10, 306–320 (2016).
Sendek, A. D. et al. Machine learning-assisted discovery of solid Li-Ion conducting materials. Chem. Mater. 31, 342–352 (2018).
Muy, S. et al. High-throughput screening of solid-state Li-ion conductors using lattice-dynamics descriptors. iScience 16, 270–282 (2019).
Zhang, Y. et al. Unsupervised discovery of solid-state lithium ion conductors. Nat. Commun. 10, 5260 (2019).
Kahle, L., Marcolongo, A. & Marzari, N. High-throughput computational screening for solid-state Li-ion conductors. Energ. Environ. Sci. https://doi.org/10.1039/c9ee02457c (2020).
He, X. et al. Crystal structural framework of lithium super‐ionic conductors. Adv. Energy Mater. https://doi.org/10.1002/aenm.201902078 (2019).
Arbi, K., Mandal, S., Rojo, J. M. & Sanz, J. Dependence of ionic conductivity on composition of fast ionic conductors Li1+xTi2-xAlx(PO4)3, 0 ≤x≤ 0.7. A parallel NMR and electric impedance study. Chem. Mater. 14, 1091–1097 (2002).
Kim, J., Kim, J., Avdeev, M., Yun, H. & Kim, S.-J. LiTa2PO8: a fast lithium-ion conductor with new framework structure. J. Mater. Chem. A 6, 22478–22482 (2018).
Wang, Q. et al. A new lithium‐ion conductor LiTaSiO5: theoretical prediction, materials synthesis, and ionic conductivity. Adv. Funct. Mater. 29, 1904232 (2019).
Xiong, S. et al. Computation‐guided design of LiTaSiO5, a new lithium ionic conductor with sphene structure. Adv. Energy Mater. 9, 1803821 (2019).
Hong, H. Y. P. Crystal structure and ionic conductivity of Li14Zn(GeO4)4 and other new Li+ superionic conductors. Mater. Res. Bull. 13, 117–124 (1978).
Bruce, P. G. & West, A. R. Phase diagram of the LISICON, solid electrolyte system, Li4GeO4 Zn2GeO4. Mater. Res. Bull. 15, 379–385 (1980).
Jain, A. et al. Commentary: The Materials Project: a materials genome approach to accelerating materials innovation. APL Mater. 1, 011002 (2013).
Ong, S. P. et al. Python materials genomics (pymatgen): a robust, open-source python library for materials analysis. Comp. Mater. Sci. 68, 314–319 (2013).
Belsky, A., Hellenbrandt, M., Karen, V. L. & Luksch, P. New developments in the Inorganic Crystal Structure Database (ICSD): accessibility in support of materials research and design. Acta Crystallogr. B: Struct. Sci. https://doi.org/10.1107/s0108768102006948 (2002).
Malik, R., Burch, D., Bazant, M. & Ceder, G. Particle size dependence of the ionic diffusivity. Nano Lett. 10, 4123–4127 (2010).
Lee, D. W. & Ok, K. M. New alkali-metal gallium selenites, AGa(SeO3)2 (A = Li, Na, K, and Cs): effect of cation size on the framework structures and macroscopic centricities. Inorg. Chem. 52, 5176–5184 (2013).
Stefano, D. D. et al. Superionic diffusion through frustrated energy landscape. Chem https://doi.org/10.1016/j.chempr.2019.07.001 (2019).
Pinsky, M. & Avnir, D. Continuous symmetry measures. 5. The classical polyhedra. Inorg. Chem. 37, 5575–5582 (1998).
Ven, A. V. D., Ceder, G., Asta, M. & Tepesch, P. D. First-principles theory of ionic diffusion with nondilute carriers. Phys. Rev. B 64, 184307 (2001).
Lee, J. et al. Unlocking the potential of cation-disordered oxides for rechargeable lithium batteries. Science 343, 519–522 (2014).
Zhang, Z. et al. Targeting superionic conductivity by turning on anion rotation at room temperature in fast ion conductors. Matter 2, 1667–1684 (2020).
Hanghofer, I., Gadermaier, B. & Wilkening, H. M. R. Fast rotational dynamics in argyrodite-type Li6PS5X (X: Cl, Br, I) as Seen by 31P nuclear magnetic relaxation—on cation–anion coupled transport in thiophosphates. Chem. Mater. 31, 4591–4597 (2019).
Zhang, Z., Roy, P.-N., Li, H., Avdeev, M. & Nazar, L. F. Coupled cation-anion dynamics enhances cation mobility in room temperature superionic solid-state electrolytes. J. Amer. Chem. Soc. https://doi.org/10.1021/jacs.9b09343 (2019).
Rong, Z. et al. Fast Mg2+ diffusion in Mo3(PO4)3O for Mg batteries. Chem. Commun. 53, 7998–8001 (2017).
Delaunay, B. Sur la sphère vide. Bull. Acad. Sci. URSS, VII. Ser. 1934, 793–800 (1934).
Daly, P. W. The Tetrahedron Quality Factors of CSDS (Max-Planck-Institut für Aeronomie, 1994).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Kresse, G. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Jain, A. et al. Formation enthalpies by mixing GGA and GGA + U calculations. Phys. Rev. B 84, 045115 (2011).
Miara, L. J., Richards, W. D., Wang, Y. E. & Ceder, G. First-principles studies on cation dopants and electrolyte cathode interphases for lithium garnets. Chem. Mater. 27, 4040–4047 (2015).
He, X., Zhu, Y., Epstein, A. & Mo, Y. Statistical variances of diffusional properties from ab initio molecular dynamics simulations. NPJ Comput. Mater. 4, 18 (2018).
Acknowledgements
This research utilized the resources of the National Energy Research Scientific Computing Center (NERSC), a US Department of Energy Office of Science User facility operated under contract no. DE-AC02-05CH11231, and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant no. ACI-1548562. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231. K. Jun gratefully acknowledges support from a a Kwanjeong Educational Foundation scholarship.
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Y.W. initially proposed the concept. K.J. carried out all of the calculations with the help of Y.X. Y.X. implemented the site identifying algorithm. Y.S. synthesized the conductor. Y.S., Y.Z. and R.K. densified the pellet. Y.S. performed the electrochemical characterization and analysed the results with Y.Z., K.J., H.K. and L.J.M. G.C., Y.W. and D.I. supervised the project. K.J., Y.S., Y.W. and G.C. wrote the manuscript with contributions and revisions from all authors.
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Supplementary Figs. 1–22, Tables 1–6, Notes 1–7 and references.
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Source Data Fig. 2
XRD data, EIS data and Arrhenius plot.
Source Data Fig. 3
Distribution of the CSM and volume.
Source Data Fig. 4
Dependence of EKRA on CSM and volume.
Source Data Fig. 5
Polyhedral packing ratio, site ratio and percentile of RR-channel dimensions.
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Jun, K., Sun, Y., Xiao, Y. et al. Lithium superionic conductors with corner-sharing frameworks. Nat. Mater. 21, 924–931 (2022). https://doi.org/10.1038/s41563-022-01222-4
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DOI: https://doi.org/10.1038/s41563-022-01222-4
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