Sodium ion conducting glasses with mixed glass formers NaI–Na2O–V2O5–B2O3: application to solid state battery

Jamal,; Venugopal, Ganesh; Shareefuddin,; Chary, M. Narasimha

doi:10.1016/s0167-577x(98)00210-9

Cited by 41 publications

(17 citation statements)

References 12 publications

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“…(1). While this phenomena has not been fully explained [2,3,7,10], increases in the ionic conductivity of up to two orders of magnitude have been observed in other MGF glasses reported in the literature [1,2]. Understanding the cause of the MGFE is crucial to the effort of engineering glasses with higher ionic conductivities and other improved physical properties.…”

Section: Introductionmentioning

confidence: 97%

“…Ion conducting glasses are an important type of solid electrolyte that may be used to answer this need. A currently unexplained change in the ionic conductivity known as the mixed glass former effect (MGFE) has been seen in many mixed glass former (MGF) glasses [1][2][3][4][5][6][7][8] such as Li 2 S + GeS 2 + GeO 2 glasses [9] and Li 2 S + SiS 2 + GeS 2 glasses [3]. This change in the ionic conductivity is non-linear and non-additive and can be observed as either a decrease or an increase with changing glass former fraction at constant modifier composition between two binary glass forming systems.…”

Section: Introductionmentioning

confidence: 99%

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The densities of mixed glass former 0.35 Na2O+0.65 [xB2O3+(1−x)P2O5] glasses related to the atomic fractions and volumes of short range structures

Christensen

Byer

Olson

et al. 2012

Journal of Non-Crystalline Solids

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Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

The densities of mixed glass former 0.35 Na2O+0.65 [xB2O3+(1−x)P2O5] glasses related to the atomic fractions and volumes of short range structures

Christensen

Byer

Olson

et al. 2012

Journal of Non-Crystalline Solids

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“…A positive MGFE with a maximum deviation from linearity at x = 0.4 has been observed in the 0.35Na 2 O + 0.65[xB 2 O 3 + (1 − x)P 2 O 5 ] glasses under study in this work and is shown in Figure 1. 10 While this phenomena has not been fully explained, 2,3,7,11 increases in the ionic conductivity of up to 2 orders of magnitude have been observed in other MGF glasses reported in the literature. 1,2 Understanding the cause of the MGFE is crucial to the effort of engineering solid electrolyte glasses with even higher ionic conductivities.…”

mentioning

confidence: 94%

Structural Studies of Mixed Glass Former 0.35Na₂O + 0.65[xB₂O₃ + (1 – x)P₂O₅] Glasses by Raman and ¹¹B and ³¹P Magic Angle Spinning Nuclear Magnetic Resonance Spectroscopies

2013

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The mixed glass former (MGF) effect (MGFE) is defined as a nonlinear and nonadditive change in the ionic conductivity with changing glass former composition at constant modifier composition. In this study, sodium borophosphate 0.35Na2O + 0.65[xB2O3 + (1 -x)P2O5], 0 ≤ x≤ 1, glasses which have been shown to exhibit a positive MGFE have been prepared and examined using Raman and 11B and 31P magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopies. Through examination of the short-range order (SRO) structures found in the ternary glasses, it was determined that the minority glass former, B for 0.1 ≤ x ≤ 0.7 and P for 0.7 ≤ x ≤ 0.9, is "overmodified" and contains more Na+ ions than would be expected from simple linear mixing of the binary sodium borate, x = 1, and sodium phosphate, x = 0, glasses, respectively. Changes in the intermediate range order (IRO) structures were suggested by changes in the NMR spectral chemical shifts and Raman spectra wavenumber shifts over the full composition range x in the Raman and MAS NMR spectra. The changes observed in the chemical shifts of 31P MAS NMR spectra with x are found to be too large to be caused solely by changing sodium modification of the phosphate SRO structural groups, and this indicates that internetwork bonding between phosphorus and boron through bridging oxygens (BOs), P-O-B, must be a major contributor to the IRO structure of these glasses. While not fully developed, a firstorder thermodynamic analysis based upon the Gibbs free energies of formation of the various SRO structural units in this system has been developed and can be used to account for the preferential formation of tetrahedral boron groups, B4, by the reaction of B3 with P2 groups to form B4 and P3 groups, respectively, where the superscript denotes the number of BOs on these units, in these glasses. This preference for B4 units appears to be a predominate cause of the changing modifier to glass former ratio with composition x in these ternary MGF glasses and appears to be associated with the large negative value of the Gibbs free energy of formation of this group. Disciplines Materials Science and Engineering | Physical Chemistry CommentsReprinted with permission from The Journal of Physical Chemistry B 117 (2013) P magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopies. Through examination of the short-range order (SRO) structures found in the ternary glasses, it was determined that the minority glass former, B for 0.1 ≤ x ≤ 0.7 and P for 0.7 ≤ x ≤ 0.9, is "overmodified" and contains more Na + ions than would be expected from simple linear mixing of the binary sodium borate, x = 1, and sodium phosphate, x = 0, glasses, respectively. Changes in the intermediate range order (IRO) structures were suggested by changes in the NMR spectral chemical shifts and Raman spectra wavenumber shifts over the full composition range x in the Raman and MAS NMR spectra. The changes observed in the chemical shifts of 31 P MAS NMR spectra with x are found to be too large to be ...

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“…Ion conducting glasses are an important type of solid electrolyte that can be used to answer this need. A currently unexplained change in the ionic conductivity known as the mixed glass former effect (MGFE) has been seen in many mixed glass former (MGF) glasses [1][2][3][4][5][6][7][8] such as Li 2 S + GeS 2 + GeO 2 glasses [9] and Li 2 S + SiS 2 + GeS 2 glasses [3]. This change in the ionic conductivity is non-linear and non-additive, and can be observed as either a decrease or an increase with changing glass former fraction at constant modifier composition between two binary systems.…”

Section: Introductionmentioning

confidence: 99%

The glass transition temperature of mixed glass former 0.35Na2O+0.65[xB2O3+(1−x)P2O5] glasses

Christensen

Byer

Olson

et al. 2012

Journal of Non-Crystalline Solids

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Sodium ion conducting glasses with mixed glass formers NaI–Na2O–V2O5–B2O3: application to solid state battery

Cited by 41 publications

References 12 publications

The densities of mixed glass former 0.35 Na2O+0.65 [xB2O3+(1−x)P2O5] glasses related to the atomic fractions and volumes of short range structures

The densities of mixed glass former 0.35 Na2O+0.65 [xB2O3+(1−x)P2O5] glasses related to the atomic fractions and volumes of short range structures

Structural Studies of Mixed Glass Former 0.35Na₂O + 0.65[xB₂O₃ + (1 – x)P₂O₅] Glasses by Raman and ¹¹B and ³¹P Magic Angle Spinning Nuclear Magnetic Resonance Spectroscopies

The glass transition temperature of mixed glass former 0.35Na2O+0.65[xB2O3+(1−x)P2O5] glasses

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Sodium ion conducting glasses with mixed glass formers NaI–Na2O–V2O5–B2O3: application to solid state battery

Cited by 41 publications

References 12 publications

The densities of mixed glass former 0.35 Na2O+0.65 [xB2O3+(1−x)P2O5] glasses related to the atomic fractions and volumes of short range structures

The densities of mixed glass former 0.35 Na2O+0.65 [xB2O3+(1−x)P2O5] glasses related to the atomic fractions and volumes of short range structures

Structural Studies of Mixed Glass Former 0.35Na2O + 0.65[xB2O3 + (1 – x)P2O5] Glasses by Raman and 11B and 31P Magic Angle Spinning Nuclear Magnetic Resonance Spectroscopies

The glass transition temperature of mixed glass former 0.35Na2O+0.65[xB2O3+(1−x)P2O5] glasses

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Structural Studies of Mixed Glass Former 0.35Na₂O + 0.65[xB₂O₃ + (1 – x)P₂O₅] Glasses by Raman and ¹¹B and ³¹P Magic Angle Spinning Nuclear Magnetic Resonance Spectroscopies