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Digestion processes and elemental analysis of oxide and sulfide solid electrolytes

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Abstract

Detailed elemental analysis is essential for a successful development and optimization of material systems and synthesis methods. This is especially relevant for Li- and Na-containing compounds, found in state-of-the-art and next-generation battery systems. Their materials’ properties and thus the final device performance strongly depend on the crystal structure, the stoichiometry, and defect chemistry, e.g., influencing charge carrier concentration and activation energies for vacancy transport. However, a detailed quantitative analysis of light elements in a heavy matrix, featuring a broad range of solubilities and vapor pressures, is often difficult and associated with large uncertainties and thus neglected in favor of just reporting the stoichiometry as “weighed in.” In this work, we report several approaches to digest and dissolve various oxide and sulfide-based materials, used in next-generation Li batteries, for elemental analysis via optical emission spectroscopy. These include the most common solid electrolytes Li-La-Ti–O, a perovskite material (LLTO), and Li-La-Zr-O which has garnet structure (LLZO). Additionally, a facile thermal digestion process is reported for a surrogate sulfide solid electrolyte (Na2S). The digestion procedures reported here are suitable for almost any laboratory environment and, when applied, will improve understanding of the synthesis-structure–property correlations needed to advanced batteries with all solid-state configurations.

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References

  1. Abreu-Sepúlveda M et al (2016) Synthesis and characterization of substituted garnet and perovskite-based lithium-ion conducting solid electrolytes. Ionics 22:317–325

    Article  Google Scholar 

  2. Okumura T et al (2011) Improvement of lithium ion conductivity for A-site disordered lithium lanthanum titanate perovskite oxides by fluoride ion substitution. J Mater Chem 21:10061–10068

    Article  CAS  Google Scholar 

  3. Han X et al (2017) Negating interfacial impedance in garnet-based solid-state Li metal batteries. Nat Mater 16:572–579

    Article  CAS  Google Scholar 

  4. Narayanan S, Hitz GT, Wachsman ED, Thangadurai V (2015) Effect of excess Li on the structural and electrical properties of garnet-type Li6La3Ta1.5Y0.5O12. J Electrochem Soc 162:A1772–A1777

    Article  CAS  Google Scholar 

  5. Thangadurai V, Weppner W (2005) Li6ALa2Ta2O12 (A = Sr, Ba): novel garnet-like oxides for fast lithium ion conduction. Adv Funct Mater 15:107–112

    Article  CAS  Google Scholar 

  6. Gordon ZD, Yang T, Gomes Morgado GB, Chan CK (2016) Preparation of nano- and microstructured garnet Li7La3Zr2O12 solid electrolytes for Li-ion batteries via cellulose templating. ACS Sus Chem & Eng 4:6391–6398

    Article  CAS  Google Scholar 

  7. Shimonishi Y et al (2011) Synthesis of garnet-type Li7−xLa3Zr2O12−1/2x and its stability in aqueous solutions. Solid State Ionics 183:48–53

    Article  CAS  Google Scholar 

  8. Thompson T et al (2015) A tale of two sites: on defining the carrier concentration in garnet-based ionic conductors for advanced li batteries. Adv Energy Mater 5:1500096

    Article  Google Scholar 

  9. Buschmann H, Berendts S, Mogwitz B, Janek J (2012) Lithium metal electrode kinetics and ionic conductivity of the solid lithium ion conductors “Li7La3Zr2O12” and Li7−xLa3Zr2−xTaxO12 with garnet-type structure. J Power Sources 206:236–244

    Article  CAS  Google Scholar 

  10. Wagner R et al (2016) Crystal structure of garnet-related Li-ion conductor Li7–3xGaxLa3Zr2O12: fast Li-ion conduction caused by a different cubic modification? Chem Mater 28:1861–1871

    Article  CAS  Google Scholar 

  11. Allen JL, Wolfenstine J, Rangasamy E, Sakamoto J (2012) Effect of substitution (Ta, Al, Ga) on the conductivity of Li7La3Zr2O12. J Power Sources 206:315–319

    Article  CAS  Google Scholar 

  12. Tsai C-L et al (2015) High conductivity of mixed phase Al-substituted Li7La3Zr2O12. J Electroceram 35:25–32

    Article  CAS  Google Scholar 

  13. Rangasamy E, Wolfenstine J, Allen J, Sakamoto J (2013) The effect of 24c-site (A) cation substitution on the tetragonal–cubic phase transition in Li7−xLa3−xAxZr2O12 garnet-based ceramic electrolyte. J Power Sources 230:261–266

    Article  CAS  Google Scholar 

  14. Ohta H et al (2012) Lithium-ion conducting La2/3−xLi3xTiO3 solid electrolyte thin films with stepped and terraced surfaces. Appl Phys Let 100:173107

    Article  Google Scholar 

  15. Pfenninger R, Struzik M, Garbayo I, Stilp E, Rupp JLM (2019) A low ride on processing temperature for fast lithium conduction in garnet solid-state battery films. Nat Energy 4:475–483

    Article  CAS  Google Scholar 

  16. Mann M et al (2021) Evaluation of scalable synthesis methods for aluminum-substituted Li7La3Zr2O12 solid electrolytes. Materials 14:6809

    Article  CAS  Google Scholar 

  17. Malkowski TF et al (2021) Role of pairwise reactions on the synthesis of Li0.3La0.57TiO3 and the resulting structure–property correlations. Inorg Chem 60:14831–14843

    Article  CAS  Google Scholar 

  18. McAuliffe RD et al (2021) Synthesis of model sodium sulfide films. J Vac Sci Tech A 39:053404

  19. Tsai C-L et al (2016) Li7La3Zr2O12 interface modification for li dendrite prevention. ACS Appl Mater Interfaces 8:10617–10626

    Article  CAS  Google Scholar 

  20. Badami P et al (2020) Highly conductive garnet-type electrolytes: access to Li6.5La3Zr1.5Ta0.5O12 prepared by molten salt and solid-state methods. ACS Appl Mater Interfaces 12:48580–48590

    Article  CAS  Google Scholar 

  21. Zheng Z, Zhang Y, Song S, Wang Y (2017) Sol–gel-processed amorphous inorganic lithium ion electrolyte thin films: sol chemistry. RSC Adv 7:30160–30165

    Article  CAS  Google Scholar 

  22. Zheng Z, Song S, Wang Y (2016) Sol-gel-processed amorphous lithium ion electrolyte thin films: structural evolution, theoretical considerations, and ion transport processes. Solid State Ion 287:60–70

    Article  CAS  Google Scholar 

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Acknowledgements

The authors would like to thank Dr. Tim Armstrong (Steward Advanced Materials—Chattanooga TN) for the commercial samples of solid electrolytes. GMV would like to thank Diana Stamberga in ORNL’s Chemical Separations Group for repeated access to the ICP used in this work and the high level of safety instilled in her laboratories. Work at ORNL (TFM, EOB, GMV – LLTO, LLZO digestion, Na2S) was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Science and Engineering. Work at Julich was conducted as part of the US-German joint collaboration on “Interfaces and Interphases In Rechargeable Li-metal based Batteries” supported by the US Department of Energy (DOE) and German Federal Ministry of Education and Research (BMBF). Financial support from the BMBF within 03XP0223A. Additionally, funding from the German Federal Ministry of Education and Research (BMBF) under grant no.: 13XP0173A (FestBatt-Oxide) and 13XP0434A (FB2-Oxide) is gratefully acknowledged. This manuscript has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE).

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Authors and Affiliations

  1. Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Thomas F. Malkowski, Ethan D. Boeding & Gabriel M. Veith

  2. Bredesen Center, University of Tennessee, Knoxville, TN, USA

    Ethan D. Boeding & Gabriel M. Veith

  3. Institute of Energy and Climate Research–Materials Synthesis and Processing (IEK-1), Forschungszentrum Jülich GmbH, Wilhelm-Johnen-Str, 52425, Jülich, Germany

    Dina Fattakhova-Rohlfing & Martin Finsterbusch

  4. Faculty of Engineering and Center for Nanointegration Duisburg-Essen (CENIDE), Universität Duisburg-Essen, Lotharstraße 1, 47057, Duisburg, Germany

    Dina Fattakhova-Rohlfing

  5. Central Institute for Engineering, Electronics and Analytics, Analytics (ZEA-3), Forschungszentrum Jülich GmbH, 52425, Jülich, Germany

    Nadine Wettengl

Authors
  1. Thomas F. Malkowski
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  2. Ethan D. Boeding
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  3. Dina Fattakhova-Rohlfing
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  4. Nadine Wettengl
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  5. Martin Finsterbusch
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  6. Gabriel M. Veith
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Correspondence to Gabriel M. Veith.

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This manuscript has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). the U.S. government retains and the publisher, by accepting the article for publication, acknowledges, that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (https://energy.gov/downloads/doe-public-access-plan)

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Malkowski, T.F., Boeding, E.D., Fattakhova-Rohlfing, D. et al. Digestion processes and elemental analysis of oxide and sulfide solid electrolytes. Ionics 28, 3223–3231 (2022). https://doi.org/10.1007/s11581-022-04536-0

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  • DOI: https://doi.org/10.1007/s11581-022-04536-0

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