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Variation in structure and Li+-ion migration in argyrodite-type Li6PS5X (X = Cl, Br, I) solid electrolytes

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Abstract

All-solid-state rechargeable lithium-ion batteries (AS-LIBs) are attractive power sources for electrochemical applications due to their potentiality in improving safety and stability over conventional batteries with liquid electrolytes. Finding a solid electrolyte with high ionic conductivity and compatibility with other battery components is a key factor in raising the performance of AS-LIBs. In this work, we prepare argyrodite-type Li6PS5X (X = Cl, Br, I) using mechanical milling followed by annealing. X-ray diffraction characterization reveals the formation and growth of crystalline Li6PS5X in all cases. Ionic conductivity of the order of 7 × 10−4 S cm−1 in Li6PS5Cl and Li6PS5Br renders these phases suitable for AS-LIBs. Joint structure refinements using high-resolution neutron and laboratory X-ray diffraction provide insight into the influence of disorder on the fast ionic conductivity. Besides the disorder in the lithium distribution, it is the disorder in the S2−/Cl− or S2−/Br− distribution that we find to promote ion mobility, whereas the large I− cannot be exchanged for S2− and the resulting more ordered Li6PS5I exhibits only a moderate conductivity. Li+ ion migration pathways in the crystalline compounds are modelled using the bond valence approach to interpret the differences between argyrodites containing different halide ions.

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References

  1. Minami K, Mizuno F, Hayashi K, Tatsumisago M (2007) Solid State Ionics 178:837–841

    Article  CAS  Google Scholar 

  2. Saienga J, Martin SW (2008) J Non-Cryst Solids 354:1475–1486

    Article  CAS  Google Scholar 

  3. Prasada Rao R, Seshasayee M (2006) J Non-Cryst Solids 352:3310–3314

    Article  CAS  Google Scholar 

  4. Beeken RB, Garbe JJ, Gillis JM, Petersen NR, Podoll BW, Stoneman MR (2005) J Phys Chem Solid 66:882–886

    Article  CAS  Google Scholar 

  5. Deiseroth H-J, Kong S-T, Eckert H, Vannahme J, Reiner C, Zaiß T, Schlosser M (2008) Angew Chem Int Ed 47(4):755–758

    Article  CAS  Google Scholar 

  6. Deiseroth H-J, Maier J, Weichert K, Nickel V, Kong S-T, Reiner C (2011) Z Anorg Allg Chem 637:1287–1294

    Article  CAS  Google Scholar 

  7. Kuhs WF, Nitsche R, Scheunemann K (1979) Mat Res Bull 14:241–248

    Article  CAS  Google Scholar 

  8. Larson AC, von Dreele RB (2000) General Structure Analysis System (GSAS). Report LAUR 86–748; Los Alamos National Laboratory, Los Alamos, NM

  9. Toby BJ (2001) J Appl Crystallogr 34:210–213

    Article  CAS  Google Scholar 

  10. Adams S (2000) J Power Source 159:200–204

    Article  Google Scholar 

  11. Adams S (2001) Acta Crystallogr B Struct Sci 57:278–287

    Article  CAS  Google Scholar 

  12. Adams S, Swenson J (2004) Solid State Ionics 175:665–669

    Article  CAS  Google Scholar 

  13. Adams S (2006) Solid State Ionics 177:1625–1630

    Article  CAS  Google Scholar 

  14. Adams S, Prasada Rao R (2009) Phys Chem Chem Phys 11:3210–3216

    Article  CAS  Google Scholar 

  15. Prasada Rao R, Tho TD, Adams S (2010) Solid State Ionics 181:1–6

    Article  CAS  Google Scholar 

  16. Adams S, Prasada Rao R (2011) Phys Stat Sol A 208(8):1746–1753

    Article  CAS  Google Scholar 

  17. Prasada Rao R, Adams S (2011) Phys Stat Sol A 208(8):1804–1807

    Article  Google Scholar 

  18. Kong S-T, Deiseroth H-J, Reiner C, Gün Ö, Neumann E, Ritter C, Zahn D (2010) Chem Eur J 16:2198–2206

    Article  CAS  Google Scholar 

  19. Pecher O, Kong S-T, Goebel T, Nickel V, Weichert K, Reiner C, Deiseroth H-J, Maier J, Haarmann F, Zahn D (2010) Chem Eur J 16:8347–8354

    Article  CAS  Google Scholar 

  20. Kong S-T, Deiseroth H-J, Maier J, Nickel V, Weichert K, Reiner C (2010) Z Anorg Allg Chem 636:1920–1924

    Article  CAS  Google Scholar 

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Acknowledgements

Financial support to R. P. R. and S. A. in the frame of the Singapore Ministry of Education Grant MOE2009-T2-1-065 is gratefully acknowledged.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, National University of Singapore, Singapore, 117576, Singapore

    Prasada Rao Rayavarapu & Stefan Adams

  2. Australian Nuclear Science and Technology Organisation, The Bragg Institute, Locked Bag 2001, Kirrawee DC, NSW, 2232, Australia

    Neeraj Sharma & Vanessa K. Peterson

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  1. Prasada Rao Rayavarapu
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  2. Neeraj Sharma
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  3. Vanessa K. Peterson
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  4. Stefan Adams
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Correspondence to Prasada Rao Rayavarapu.

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Rayavarapu, P.R., Sharma, N., Peterson, V.K. et al. Variation in structure and Li+-ion migration in argyrodite-type Li6PS5X (X = Cl, Br, I) solid electrolytes. J Solid State Electrochem 16, 1807–1813 (2012). https://doi.org/10.1007/s10008-011-1572-8

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  • DOI: https://doi.org/10.1007/s10008-011-1572-8

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