Abstract
Rechargeable lithium batteries have long been considered an attractive alternative power source for a wide variety of applications. Safety and stability1 concerns associated with solvent-based electrolytes has necessitated the use of lithium intercalation materials (rather than lithium metal) as anodes, which decreases the energy storage capacity per unit mass. The use of solid lithium ion conductors—based on glasses, ceramics or polymers—as the electrolyte would potentially improve the stability of a lithium-metal anode while alleviating the safety concerns. Glasses and ceramics conduct via a fast ion mechanism, in which the lithium ions move within an essentially static framework. In contrast, the motion of ions in polymer systems is similar to that in solvent-based electrolytes—motion is mediated by the dynamics of the host polymer, thereby restricting the conductivity to relatively low values. Moreover, in the polymer systems, the motion of the lithium ions provides only a small fraction of the overall conductivity2, which results in severe concentration gradients during cell operation, causing premature failure3. Here we describe a class of materials, prepared by doping lithium ions into a plastic crystalline matrix, that exhibit fast lithium ion motion due to rotational disorder and the existence of vacancies in the lattice. The combination of possible structural variations of the plastic crystal matrix and conductivities as high as 2 × 10-4 S cm-1 at 60 °C make these materials very attractive for secondary battery applications.
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References
Gray,F. M. Solid Polymer Electrolytes: Fundamentals and Technological Applications 13 (VCH, New York, 1991).
Ma,Y. et al. The measurement of a complete set of transport properties for a concentrated solid polymer electrolyte solution. J. Electrochem. Soc. 142, 1859–1868 (1995).
Doeff,M. M., Ferry,A., Ma,Y., Ding,L. & De Jonghe,L. C. Effect of electrolyte composition on the performance of sodium/polymer cells. J. Electrochem. Soc. 144, L20–L22 (1997).
Wong,S. et al. Towards elucidating microscopic structural changes in Li-ion conductors Li(1+y)Ti(2-y)Aly(PO4)3 and Li1+yTi2+yAl(PO4)3-x(MO4)x (M = V and Nb): x-ray and 27Al and 31P NMR studies. J. Mater. Chem. 8, 2199–2203 (1998).
Adachi,G-Y., Imanaka,N. & Aono,H. Fast Li+ conducting ceramic electrolytes. Adv. Mater. 8, 127–134 (1996).
Timmermans,J. Plastic crystals: a historical review. J. Phys. Chem. Solids 18, 1–8 (1961).
Handra,D., Helmes,J. H. & Majumdar,A. Ionic conductivity in ordered and disordered phases of plastic crystals. J. Electrochem. Soc. 141, 1921–1927 (1994).
Hattori,M., Fukada,S., Nakamura,D. & Ikeda,R. Studies of the anisotropic self-diffusion and reorientation of butyl ammonium cations in the rotator phase of butyl ammonium chloride using 1H magnetic resonance, electrical conductivity and thermal measurements. J. Chem. Soc. Faraday Trans. 86, 3777–3783 (1990).
Ishida,H., Furukawa,Y., Kashino,S., Sato,S. & Ikeda,R. Phase transitions and ionic motions in solid trimethylethylammonium iodide studied by 1H and 127I NMR, electrical conductivity, X-ray diffraction and thermal analysis. Ber. Bunsenges. Phys. Chem. 100, 433–439 (1996).
Tanabe,T., Nakamura,D. & Ikeda,R. Novel ionic plastic crystal phase of [(CH3)4N]SCN obtainable above 455K studied by proton magnetic resonance, electrical conductivity and thermal measurements. J. Chem. Soc. Faraday Trans. 87, 987–990 (1991).
Shimizu,T., Tanaka,S., Onoda-Yamamuro,N., Ishimaru,S. & Ikeda,R. New rotator phase revealed in di-n-alkylammonium bromides studies by solid state NMR, powder XRD, electrical conductivity and thermal measurements. J. Chem. Soc. Faraday Trans. 93, 321–326 (1997).
Cooper,E. I. & Angell,C. A. Ambient temperature plastic crystal fast ion conductors (PLICFICS). Solid State Ionics 18/19, 570–576 (1986).
Aronson,R. et al. Fast ion conductors with rotating sulphate ions. J. Phys. Colloq. C6 41, 35–37 (1980).
Aronson,R., Knape,H. E. G. & Torell,L. M. Brillouin spectra of the solid electrolyte Li2SO4. J. Chem. Phys. 77, 677–680 (1982).
Borgesson,L. & Torell,L. M. Reorientational motion in superionic sulphates: A Raman linewidth study. Phys. Rev. B 32, 2471–2477 (1985).
MacFarlane,D. R., Sun,J., Forsyth,M., Meakin,P. & Amini,N. Pyrrolidinium imides: a new family of molten salts and conductive plastic crystal phases. J. Phys. Chem. 103, 4164–4170 (1999).
Sun,J., Forsyth,M. & MacFarlane,D. R. Room temperature molten salts based on the quarternary ammonium ion. J. Phys. Chem. 102, 8858–8864 (1998).
Sylla,S., Sanchez,J-Y. & Armand,M. Electrochemical study of linear and crosslinked POE-based polymer electrolytes. Electrochim. Acta 37, 1699–1701 (1992).
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MacFarlane, D., Huang, J. & Forsyth, M. Lithium-doped plastic crystal electrolytes exhibiting fast ion conduction for secondary batteries. Nature 402, 792–794 (1999). https://doi.org/10.1038/45514
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DOI: https://doi.org/10.1038/45514
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