Structure of amorphous materials in the NASICON system Na1+xTi        2SixP3-xO12.

Rita Mendes Da Silva; Anita Zeidler; Henrik Bradtmüller; Hellmut Eckert; Henry E Fischer; Chris J Benmore; Philip S Salmon

doi:10.1088/1361-648X/acc8af

Structure of amorphous materials in the NASICON system Na1+xTi 2SixP3-xO12.

Rita Mendes Da Silva, Anita Zeidler, Henrik Bradtmüller, Hellmut Eckert, Henry E Fischer, Chris J Benmore, Philip S Salmon

Research output: Contribution to journal › Article › peer-review

Abstract

The structure of glasses in the sodium (Na) super-ionic conductor (NASICON) system Na1+xTi 2Si x P3-xO 12 with x= 0.8 and x= 1.0 was explored by combining neutron and high-energy x-ray diffraction with 29Si, 31P and 23Na solid-state nuclear magnetic resonance (NMR) spectroscopy. The 29Si magic angle spinning (MAS) NMR spectra reveal that the silica component remains fully polymerized in the form of Si 4units, i.e. the silicon atoms are bound to four bridging oxygen atoms. The 31P{ 23Na} rotational echo adiabatic passage double resonance (REAPDOR) NMR data suggest that the 31P MAS NMR line shape originates from four-coordinated P n units, where n= 1, 2 or 3 is the number of bridging oxygen atoms per phosphorus atom. These sites differ in their 31P- 23Na dipolar coupling strengths. The results support an intermediate range order scenario of a phosphosilicate mixed network-former glass in which the phosphate groups selectively attract the Na +modifier ions. Titanium takes a sub-octahedral coordination environment with a mean Ti-O coordination number of 5.17(4) for x= 0.8 and 4.86(4) for x= 1.0. A mismatch between the P-O and Si-O bond lengths of 8% is likely to inhibit the incorporation of silicon into the phosphorus sites of the NASICON crystal structure.

Original language	English
Article number	274002
Number of pages	9
Journal	Journal of physics. Condensed matter : an Institute of Physics journal
Volume	35
Issue number	27
DOIs	https://doi.org/10.1088/1361-648X/acc8af
Publication status	Published - 12 Jul 2023

Bibliographical note

We are grateful to Adriana M Nieto-Muñoz and Ana Candida M. Rodrigues (Universidade Federal de São Carlos) for providing the glassy samples. R M D S acknowledges funding and support from the Royal Society (Grant No. RGF/EA/180060). A Z was supported by a Royal Society-EPSRC Dorothy Hodgkin Research Fellowship. Support by FAPESP, Project 2013/07793-6, is gratefully acknowledged. H B also thanks FAPESP for support for a post-doctoral fellowship, process 2019/26399-3. We acknowledge use of the Engineering and Physical Sciences Research Council (EPSRC) funded National Chemical Database Service hosted by the Royal Society of Chemistry. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.

Data availability statement
The data that support the findings of this study are openly available at the following URL/DOI: https://doi.org/10.15125/BATH-01226 [44]. The measured neutron diffraction data sets are available from [45].

Keywords

NASICON
amorphous materials
neutron and x-ray diffraction
solid-state NMR
structure

ASJC Scopus subject areas

General Materials Science
Condensed Matter Physics

Access to Document

10.1088/1361-648X/acc8afLicence: CC BY

Cite this

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title = "Structure of amorphous materials in the NASICON system Na1+xTi 2SixP3-xO12.",

abstract = "The structure of glasses in the sodium (Na) super-ionic conductor (NASICON) system Na1+xTi 2Si x P3-xO 12 with x= 0.8 and x= 1.0 was explored by combining neutron and high-energy x-ray diffraction with 29Si, 31P and 23Na solid-state nuclear magnetic resonance (NMR) spectroscopy. The 29Si magic angle spinning (MAS) NMR spectra reveal that the silica component remains fully polymerized in the form of Si 4units, i.e. the silicon atoms are bound to four bridging oxygen atoms. The 31P{ 23Na} rotational echo adiabatic passage double resonance (REAPDOR) NMR data suggest that the 31P MAS NMR line shape originates from four-coordinated P n units, where n= 1, 2 or 3 is the number of bridging oxygen atoms per phosphorus atom. These sites differ in their 31P- 23Na dipolar coupling strengths. The results support an intermediate range order scenario of a phosphosilicate mixed network-former glass in which the phosphate groups selectively attract the Na +modifier ions. Titanium takes a sub-octahedral coordination environment with a mean Ti-O coordination number of 5.17(4) for x= 0.8 and 4.86(4) for x= 1.0. A mismatch between the P-O and Si-O bond lengths of 8% is likely to inhibit the incorporation of silicon into the phosphorus sites of the NASICON crystal structure. ",

keywords = "NASICON, amorphous materials, neutron and x-ray diffraction, solid-state NMR, structure",

author = "{Mendes Da Silva}, Rita and Anita Zeidler and Henrik Bradtm{\"u}ller and Hellmut Eckert and Fischer, {Henry E} and Benmore, {Chris J} and Salmon, {Philip S}",

note = "We are grateful to Adriana M Nieto-Mu{\~n}oz and Ana Candida M. Rodrigues (Universidade Federal de S{\~a}o Carlos) for providing the glassy samples. R M D S acknowledges funding and support from the Royal Society (Grant No. RGF/EA/180060). A Z was supported by a Royal Society-EPSRC Dorothy Hodgkin Research Fellowship. Support by FAPESP, Project 2013/07793-6, is gratefully acknowledged. H B also thanks FAPESP for support for a post-doctoral fellowship, process 2019/26399-3. We acknowledge use of the Engineering and Physical Sciences Research Council (EPSRC) funded National Chemical Database Service hosted by the Royal Society of Chemistry. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Data availability statement The data that support the findings of this study are openly available at the following URL/DOI: https://doi.org/10.15125/BATH-01226 [44]. The measured neutron diffraction data sets are available from [45].",

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AU - Bradtmüller, Henrik

AU - Eckert, Hellmut

AU - Fischer, Henry E

AU - Benmore, Chris J

AU - Salmon, Philip S

N1 - We are grateful to Adriana M Nieto-Muñoz and Ana Candida M. Rodrigues (Universidade Federal de São Carlos) for providing the glassy samples. R M D S acknowledges funding and support from the Royal Society (Grant No. RGF/EA/180060). A Z was supported by a Royal Society-EPSRC Dorothy Hodgkin Research Fellowship. Support by FAPESP, Project 2013/07793-6, is gratefully acknowledged. H B also thanks FAPESP for support for a post-doctoral fellowship, process 2019/26399-3. We acknowledge use of the Engineering and Physical Sciences Research Council (EPSRC) funded National Chemical Database Service hosted by the Royal Society of Chemistry. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Data availability statement The data that support the findings of this study are openly available at the following URL/DOI: https://doi.org/10.15125/BATH-01226 [44]. The measured neutron diffraction data sets are available from [45].

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N2 - The structure of glasses in the sodium (Na) super-ionic conductor (NASICON) system Na1+xTi 2Si x P3-xO 12 with x= 0.8 and x= 1.0 was explored by combining neutron and high-energy x-ray diffraction with 29Si, 31P and 23Na solid-state nuclear magnetic resonance (NMR) spectroscopy. The 29Si magic angle spinning (MAS) NMR spectra reveal that the silica component remains fully polymerized in the form of Si 4units, i.e. the silicon atoms are bound to four bridging oxygen atoms. The 31P{ 23Na} rotational echo adiabatic passage double resonance (REAPDOR) NMR data suggest that the 31P MAS NMR line shape originates from four-coordinated P n units, where n= 1, 2 or 3 is the number of bridging oxygen atoms per phosphorus atom. These sites differ in their 31P- 23Na dipolar coupling strengths. The results support an intermediate range order scenario of a phosphosilicate mixed network-former glass in which the phosphate groups selectively attract the Na +modifier ions. Titanium takes a sub-octahedral coordination environment with a mean Ti-O coordination number of 5.17(4) for x= 0.8 and 4.86(4) for x= 1.0. A mismatch between the P-O and Si-O bond lengths of 8% is likely to inhibit the incorporation of silicon into the phosphorus sites of the NASICON crystal structure.

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Structure of amorphous materials in the NASICON system Na1+xTi 2SixP3-xO12.

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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Data sets for "Structure of amorphous materials in the NASICON system Na_{1+x}Ti_2Si_xP_{3-x}O_{12}"

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Structure of amorphous materials in the NASICON system Na1+xTi 2SixP3-xO12.

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

Data sets for "Structure of amorphous materials in the NASICON system Na_{1+x}Ti_2Si_xP_{3-x}O_{12}"

Cite this