Correlation of ion dynamics with characteristic length scales and network structural units in bismuth borate glasses

Shaw, A.; Ghosh, A.

doi:10.1063/1.4821154

Cited by 15 publications

(15 citation statements)

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“…[30][31][32][33][34][35] Additionally, there has been some efforts in extracting relevant length scales (see Appendix A) by analyzing the ionic conductivity and dielectric permittivity spectra in alkali ion based MGF systems. 17,[36][37][38] The main findings on changes in structural units and bonds as a function of relative composition of glass formers in borophosphate glasses containing Li2O or Na2O as network modifiers is that hetero-atomic bonds such as P-O-B are preferred to homo-atomic bonds such as P-O-P and B-O-B, for up to about 30 mol% borate content. This information was made possible by X-Ray Diffraction (XRD) technique and XPS spectroscopy, 27 or by using Raman and magic-angle spinning (MAS) NMR experiments.…”

Section: Introductionmentioning

confidence: 99%

“…[62][63] If the Haven ratio is assumed to be unity, since this is a hard to determine quantity, what this relation yields is < R 2 ( ) >, the mean-square displacement of the center of charge of the mobile ions. One thus constructs a plot of 〈R 2 ( )〉 versus log(t), and can read off the value of Another length scale which is relevant is the spatial extent of localized diffusion, and is calculated as 〈r 2 (∞)〉 1/2 from scaling of the real part of the permittivity spectra 7,45,46 using the MIGRATION concept; or in a model independent way from an analysis of the permittivity spectra 36,38,62,63 as 〈R 2 (∞)〉 1/2 . This length scale gives information on the nature of the localized excursions that the ion makes, and hence is closely related to local structure.…”

mentioning

confidence: 99%

“…In contrast to the early findings of Sidebottom et al in 1997, 58 length scales in the other works were found to be several Angstroms in magnitude. 36,38,62,63 However, in MGFE systems studied by Zielniok et al, 16 as well as a re-analysis of their data by modelling the permittivity spectra Banhatti et al, 17 The proportionality constant of decay along the single-particle and many-particle routes is given by the relation. = −ln (W(∞)).…”

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confidence: 99%

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Insights from Local Network Structures and Localized Diffusion on the Ease of Lithium Ion Transport in Two Mixed Glass-Former Systems

et al. 2017

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The conductivity enhancement observed in the two glass systems, A: 40Li2O-(60-x)P2O5-xGeO2 and B: 40Li2O-10B2O3-(50-x)P2O5-xGeO2, as germanate content is increased from 0 to 25 mol% confirms the positive mixed glass-former effect (MGFE) in these systems. In this study, we further employ state-of-art NMR techniques along with Raman spectra to probe the local network structures. We use the MIGRATION concept to model the experimental conductivity and permittivity spectra obtained from impedance spectroscopy to understand scaling features of spectra and to calculate the value of the spatial extent of the localized diffusion of the lithium ion. As x increases from 0 to 25 mol%, for system A, a continuous increase of the POGe cross linkages as well as a continuous and strong modification of the phosphate network is observed. In system B, deeper analysis of the 31 P MAS-NMR experiments done using 2D 11 B/ 11 B homo-nuclear and 11 B/ 31 P hetero-nuclear NMR is used to determine the nature of the BOB linkages as well as that of POB linkages. Modelling of the conductivity spectra shows that the shape parameter of the spectra remains the same for both systems and for all compositions, a feature typical for MGFE. Further, correlating the trends of the spatial extent of localized diffusion with that gleamed from the local structures, we infer that as relative germanate content increases, in the ternary glass (system A) the ease of mobility of the Li + ion is enhanced while in the quaternary glass (system B, x > 0) it is somewhat hindered. Recently, using high-energy X-Ray photons in diffraction (HEXRD) on a synchrotron and neutron diffraction on a spallation source, Hoppe et al. 34 have detected six coordinated Ge in the structure of Na2O-GeO2-P2O5 glasses with high P2O5 contents and up to 24 mol% GeO2 fraction. Using thermal analysis, Raman, 31 P-MAS NMR and 23 Na NMR spectroscopy in the system (M2O)0.33[(Ge2O4)x(P2O5)1-x]0.67 (M = Na, K) Behrends & Eckert 35 infer that at low Ge2O4 contents (x = 0.2), the structure is dominated by pyrophosphate chains and unmodified Ge-O-Ge bonded four-membered ring units. At higher germanate contents hetero-atomic P-O-Ge linkages dominate. In general, it is found that the phosphate network is modified by the alkali ion preferentially, resulting in partially clustered cation distributions. The authors conclude that their study provides only an indirect confirmation of the germanate anomaly.

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Section: Introductionmentioning

confidence: 99%

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Insights from Local Network Structures and Localized Diffusion on the Ease of Lithium Ion Transport in Two Mixed Glass-Former Systems

et al. 2017

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“…Though no specific correlation is identified between the σ dc conductivity and <R 2 (t p )>, the observed high ionic conductivity for NAPS-7.5 glass can be explained considering the highest <R 2 (t p )> value observed for the same glass. It has been reported for several glass compositions that the increase in the concentration of non-bridging oxygen decreases the <R 2 (t p )> as a consequence increases the dc-conductivity (Shaw and Ghosh, 2013;Chatterjee et al, 2020). On the contrary, it has also been identified that the increase in <R 2 (t p )> increases the dcconductivity due to structural modifications in the network structure of glass (Sklepić et al, 2021).…”

Section: Structure and Conductivity Correlation Through The Characteristic Displacement Curvesmentioning

confidence: 99%

Structure and Conductivity Correlation in NASICON Based Na3Al2P3O12 Glass: Effect of Na2SO4

et al. 2022

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Identifying the factors influencing the movement of sodium cations (Na+) in glasses accelerates the possible options of glass-based solid electrolyte materials for their applications as a promising electrolyte material in sodium-ion batteries. Nevertheless, due to the poor correlation between the structure and conductivity in glass materials, identifying the factors governing the conductivity still exists as a challenging task. Herein, we have investigated the DC-conductivity variations by correlating the structure and conductivity in sodium superionic conductor (NASICON) based Na3Al2P3O12 (NAP) glass (mol%: 37.5 P2O5—25.0 Al2O3—37.5 Na2O) due to the successive substitution of Na2SO4 for Al2O3. Structural variations have been identified using the Raman and magic-angle spinning nuclear magnetic resonance (MAS-NMR) (for 31P, 23Na, and 27Al nuclei) and conductivity measurements have been done using the impedance spectroscopy. From the ac-conductivity spectra, the correlations between mean square displacement (MSD) and dc-conductivity and between the Na+ concentration and dc-conductivity have also been evaluated. Raman spectra reveal that the increase in the Na2SO4 concentration increases the number of isolated SO42− sulfate groups that are charge compensated by the Na+ cations in the NAP glass. MAS-NMR spectra reveal that the increase in Na2SO4 concentration increases the concentration of non-bridging oxygens and further neither S-O-P nor S-O-Al bonds are formed. Impedance spectroscopy reveals that, at 373 K, the DC conductivity of the NAP glass increases with increasing the Na2SO4 up to 7.5 mol% and then decreases with the further increase. In the present study, we have shown that the mobility of sodium cations played a significant role in enhancing the ionic-conductivity. Further, we have shown that inter-ionic Coulombic interactions and the structural modification with the formation of SO42− units significantly influence the critical hopping length < R2 (tp)> of the sodium cations and consequently the mobility and the ionic conductivity. The present study clearly indicates that, based on the compositions, glass materials can also be treated as strong-electrolyte materials.

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“…The electrostatic binding energy (E b ) is the energy required to remove a mobile cation from its non-bridging oxygen site and is given by the following relation [27,28] (3)…”

Section: Si and 7 LI Solid-state Nuclear Magnetic Resonance (Nmr)mentioning

confidence: 99%

Structure and ionic conductivity of nitrated lithium disilicate (LiSiON) glasses

Singh

Schneider

Kundu

et al. 2018

Materials Chemistry and Physics

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Lithium disilicate is a critical glass forming composition as it is the basis of some glass-ceramics and it is also a model glass for the study of homogeneous and heterogeneous crystal nucleation.Incorporation of nitrogen in this glass significantly changes its structure and affects different properties. In this paper, nitrided lithium disilicate glasses were prepared by partial substitution of oxygen up to 6 atm % N/(N+O). The modification of the silicate glass structure with nitrogen has been confirmed by Fourier transform infrared reflection (FTIR) spectroscopy. 29 Si NMR and 7 Li NMR have also been used to investigate the structural changes due to nitrogen incorporation. Substitution of oxygen by nitrogen with a higher coordination number (three) increases the connectivity of the glass. In fact, our NMR results indicate that nitrogen incorporation changes the Q n distribution (n = average number of bridging oxygens to silicon) of the silicate structural units: SiNO 3 , SiN 2 O 2 and SiN 3 O, whereas there is no detectable change in the Li environment. ACCEPTED MANUSCRIPT 2We measured the ionic (Li + ) conductivity by impedance spectroscopy and found that the incorporation of nitrogen leads to a decrease in the activation energy for conduction, resulting in an increase of up to four-fold in the ionic conductivity of the most nitrided glass. We explained this high conductivity by the Anderson and Stuart model. This work provides renewed interest in improving and understanding the ionic conductivity in oxynitride glasses.

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Correlation of ion dynamics with characteristic length scales and network structural units in bismuth borate glasses

Cited by 15 publications

References 38 publications

Insights from Local Network Structures and Localized Diffusion on the Ease of Lithium Ion Transport in Two Mixed Glass-Former Systems

Insights from Local Network Structures and Localized Diffusion on the Ease of Lithium Ion Transport in Two Mixed Glass-Former Systems

Structure and Conductivity Correlation in NASICON Based Na3Al2P3O12 Glass: Effect of Na2SO4

Structure and ionic conductivity of nitrated lithium disilicate (LiSiON) glasses

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