IR, Raman, and NMR Studies of the Short-Range Structures of 0.5Na2S + 0.5[xGeS2 + (1–x)PS5/2] Mixed Glass-Former Glasses

dc.contributor.author Bischoff, Christian
dc.contributor.author Martin, Steve
dc.contributor.author Schuller, Katherine
dc.contributor.author Dunlap, Nathan
dc.contributor.author Martin, Steve
dc.contributor.department Materials Science and Engineering
dc.date 2018-02-14T17:30:24.000
dc.date.accessioned 2020-06-30T06:06:56Z
dc.date.available 2020-06-30T06:06:56Z
dc.date.copyright Wed Jan 01 00:00:00 UTC 2014
dc.date.embargo 2013-11-04
dc.date.issued 2014-01-21
dc.description.abstract <p>A nonlinear and nonadditive composition-dependent change of the ionic conductivity in mixed glass-former (MGF) glasses when one glass former, such as PS<sub>5/2</sub>, is replaced by a second glass former, such as GeS<sub>2</sub>, at constant alkali modifier concentrations, such as Na<sub>2</sub>S, is known as the mixed glass-former effect (MGFE). Alkali ion conducting glasses are of particular interest for use as solid electrolytes in alkali-based all-solid-state batteries because sulfide amorphous materials have significantly higher alkali ion conductivities than their oxide glass counterparts. In this study of the ternary MGF system Na<sub>2</sub>S + GeS<sub>2</sub> + PS<sub>5/2</sub>, we report the careful structural characterization of these glasses using a combination of vibrational, infrared (IR), Raman, and nuclear magnetic resonance (NMR) spectroscopies. Our measurements of the 0.5Na<sub>2</sub>S + 0.5[<em>x</em>GeS<sub>2</sub> + (1–<em>x</em>)PS<sub>5/2</sub>] MGF system show that this glass system exhibits a strongly negative MGFE and non-Arrhenius ionic conductivities. While this negative MGFE in the Na<sup>+</sup> ion conductivity makes these glasses less attractive for use in solid-state Na batteries, the structural origin of this effect is important to better understand the mechanisms of ion conduction in the glassy state. For these reasons, we have examined the structures of ternary 0.5Na<sub>2</sub>S + 0.5[<em>x</em>GeS<sub>2</sub> + (1–<em>x</em>)PS<sub>5/2</sub>] glasses using Raman, IR, and <sup>31</sup>P MAS NMR spectroscopies. In these studies, it is found that the substitution of PS<sub>5/2</sub> by GeS<sub>2</sub>, that is, increasing <em>x</em>, leads to unequal sharing of the Na<sup>+</sup> in these glasses. Thus, in all MGF compositions, phosphorus groups are associated with a disproportionately larger fraction, <em>f</em><sub>Na(P)</sub> > 0.5(1 – <em>x</em>), of the Na<sup>+</sup> ions while the germanium groups are found to be Na<sup>+</sup>-deficient relative to the total amount of Na<sup>+</sup> present in the glass, that is, <em>f</em><sub>Na(Ge)</sub> < 0.5<em>x</em>. From the spectroscopic study of these glasses, a short-range order (SRO) structural model is developed for these glasses and is based on the germanium and phosphorus SRO groups in these glasses as a first step in understanding the unique negative MGFE and non-Arrhenius behavior in the Na<sup>+</sup> ion conductivity in these glasses.</p>
dc.description.comments <p><em></em>Reprinted with permission from J. Phys. Chem. B, 2014, 118 (7), pp 1943–1953 <a href="http://dx.doi.org/10.1021/jp4111053" target="_blank">doi: 10.1021/jp4111053</a>. Copyright 2014 American Chemical Society.</p>
dc.format.mimetype application/pdf
dc.identifier archive/lib.dr.iastate.edu/mse_pubs/154/
dc.identifier.articleid 1154
dc.identifier.contextkey 6153578
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath mse_pubs/154
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/55482
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/mse_pubs/154/0-2013_Martin_IRRaman_License.pdf|||Fri Jan 14 20:40:19 UTC 2022
dc.source.bitstream archive/lib.dr.iastate.edu/mse_pubs/154/1-2014_IRRaman_Martin.pdf|||Fri Jan 14 20:40:19 UTC 2022
dc.source.bitstream archive/lib.dr.iastate.edu/mse_pubs/154/2014_IRRaman_Martin.pdf|||Fri Jan 14 20:40:21 UTC 2022
dc.source.uri 10.1021/jp4111053
dc.subject.disciplines Materials Science and Engineering
dc.title IR, Raman, and NMR Studies of the Short-Range Structures of 0.5Na2S + 0.5[xGeS2 + (1–x)PS5/2] Mixed Glass-Former Glasses
dc.type article
dc.type.genre article
dspace.entity.type Publication
relation.isAuthorOfPublication e0385671-f8e7-4ceb-ba14-162c8acd29dd
relation.isOrgUnitOfPublication bf9f7e3e-25bd-44d3-b49c-ed98372dee5e
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