NMR investigations unveil phase composition–property correlations in Sr0.55Na0.45SiO2.775 fast ion conductor

Rao, P. Krishna; Pahari, Bholanath; Shivanand, M.; Shet, Tukaram; Ramanathan, K. V.

doi:10.1016/j.ssnmr.2017.05.001

Cited by 4 publications

(7 citation statements)

References 33 publications

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“…In NZSP/NS‐10 composite sample, a third small peak at −93.9 ppm is developed. Based on the published results 29 , we assigned this line as crystalline α‐Na 2 Si 2 O 5 , which arise due to partial recrystallization of amorphous‐Na 2 Si 2 O 5 . This corroborates the XRD pattern of NZSP/NS‐10, showing additional Bragg's peaks from the crystalline α‐Na 2 Si 2 O 5 phase.…”

Section: Resultsmentioning

confidence: 93%

“…It is reported that the amorphous‐Na 2 Si 2 O 5 gradually crystallizes into the poorly conducting crystalline Na 2 Si 2 O 5 phase at elevated temperatures (above 600°C) 25 . Depending on the temperature history, it may recrystalline into one or many forms out of eight polymorphs of Na 2 Si 2 O 5 26, 29 . An attempt was made to analyze the XRD pattern of NZSP/NS‐ x composites with NASICON, ZrO 2 , and crystalline Na 2 Si 2 O 5 phases.…”

Section: Resultsmentioning

confidence: 99%

“…u. first gradually increases with increasing NS wt.%, reaches to maximum for NZSP/NS-7.5, and later it slightly decreases. Figure 2 presents 29 Si MAS NMR spectra for NZSP, NZSP/NS-5.0, and NZSP/NS-10 samples. As can be seen from Figure 2, the 29 RT 31 P MAS NMR spectra taken for the NZSP, NZSP/NS-5.0, and NZSP/NS-10 samples are presented in Figure 3.…”

Section: Resultsmentioning

confidence: 99%

“…Figure 2 presents 29 Si MAS NMR spectra for NZSP, NZSP/NS-5.0, and NZSP/NS-10 samples. As can be seen from Figure 2, the 29 RT 31 P MAS NMR spectra taken for the NZSP, NZSP/NS-5.0, and NZSP/NS-10 samples are presented in Figure 3. The 31 P spectrum of all three samples displays a slightly asymmetric peak at −11.1 ppm which can be ascribed to PO 4 environments of NASICON structure.…”

Section: Resultsmentioning

confidence: 99%

“…Samples were spun at 8 kHz and spectra were taken after a 𝜋∕2 pulse. For the recording of 29 Si NMR spectrum, a pulse of width 3.0 μs and a time interval (between successive scans) of 120 s were used, whereas for 31 P NMR spectrum, a pulse of width 3.5 μs and a time interval of 900 s were used. The 29 Si and 31 P chemical shifts are given relative to tetramethylsilane and 85% aqueous H 3 PO 4 , respectively.…”

Section: Introductionmentioning

confidence: 99%

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High Na⁺ conducting Na₃Zr₂Si₂PO₁₂/Na₂Si₂O₅ composites as solid electrolytes for Na⁺ batteries

et al. 2022

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Sodium superionic conductor Na3Zr2Si2PO12 (NZSP) is a promising material as a solid electrolyte for sodium‐ion batteries. The highest conductivity of ∼1.0 mS/cm at room temperature (RT) was reported for the compound with a Na content of approximately 3.3 per formula unit (f. u.) and when the material is synthesized with a final sintering temperature ≥1220°C. Herein, we propose a new synthesis method to enhance the conductivity of the NZSP by liquid‐phase sintering with the optimum amount of additive of amorphous‐Na2Si2O5. In this regard, a series of composite materials were prepared by mixing Na3Zr2Si2PO12 with amorphous‐Na2Si2O5 (NZSP/NS‐x wt.%; with x = 0.0, 2.5, 5.0, 7.5, 10.0) and sintering at a lower temperature of 1150°C. Enhanced conductivity of 1.7 mS/cm at RT has been achieved for the Na3Zr2Si2PO12/Na2Si2O5‐5.0 wt.% (NZSP/NS‐5.0) composite. The effects of additives on the NZSP phase formation, microstructure, and ion conductivity have been investigated by XRD, MAS NMR, SEM, and impedance spectroscopy. Our study demonstrates that the higher conductivity of the NZSP/NS‐5.0 composite is caused by the combined effect of increased Na content in the NZSP phase (by diffusion of Na+ ions from the liquid phase of NS to bare NZSP phase), higher density, and microstructures with lesser pores.

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Section: Resultsmentioning

confidence: 93%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

High Na⁺ conducting Na₃Zr₂Si₂PO₁₂/Na₂Si₂O₅ composites as solid electrolytes for Na⁺ batteries

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Electrochemical and degradation study of Sr0.6Na0.4SiO3-δ

Sood

Kaswan

Singh

et al. 2018

J Solid State Electrochem

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Associating High Oxide-Ion Conductivity and Conduction Mechanisms with Local Atomic Environments in Na_0.5Bi_0.5–xTi_1–yMg_yO_3−δ

et al. 2021

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Oxide-ion conductors are of high interest in electrochemical devices such as solid-oxide fuel cells, oxygen sensors, and separation membranes. In this paper, high oxide-ion conductivity and associated ion conduction mechanism in perovskite-type oxides Na0.5Bi0.5–x Ti1–y Mg y O3–1.5x–y (for x = 0.0 and y = 0.0, x = 0.01 and y = 0.02, x = 0.01 and y = 0.04) are investigated systematically. Na0.5Bi0.5TiO3 ceramic is a poor conductor, whereas Na0.5Bi0.49Ti0.98Mg0.02O2.965 and Na0.5Bi0.49Ti0.96Mg0.04O2.945 ceramics are excellent oxide-ion conductors at 500 °C. While the Rietveld refinements of powder X-ray diffraction data using the monoclinic Cc space group and the rhombohedral R3c space group showed reasonably similar quality of fits, extended X-ray absorption fine structure (EXAFS) data could be fitted only with the monoclinic Cc structure at room temperature for all three ceramics. Extensive EXAFS investigations have also been used to probe the local environments of Bi and Ti atoms directly and reveal the ordering of Bi3+/Na+, displacements of the cations, oxygen-vacancy generation, and their migration pathways. Our EXAFS results demonstrate Bi- and Na-rich planes formation due to short-range ordering of Bi3+/Na+ in the perovskite units. Oxygen vacancies were found to be located in the Bi-rich planes. 23Na magic-angle spinning NMR experiments indicate that the local environments of Na atoms are disordered. The present work also provides an insight into the dramatically improved conducting behavior of Na0.5Bi0.49Ti0.98Mg0.02O2.965 and Na0.5Bi0.49Ti0.96Mg0.04O2.945 ceramics in terms of the local, long-range, and microstructure, which can be exploited to develop design principles for the syntheses of related oxides with even improved properties.

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NMR investigations unveil phase composition–property correlations in Sr0.55Na0.45SiO2.775 fast ion conductor

Cited by 4 publications

References 33 publications

High Na⁺ conducting Na₃Zr₂Si₂PO₁₂/Na₂Si₂O₅ composites as solid electrolytes for Na⁺ batteries

High Na⁺ conducting Na₃Zr₂Si₂PO₁₂/Na₂Si₂O₅ composites as solid electrolytes for Na⁺ batteries

Electrochemical and degradation study of Sr0.6Na0.4SiO3-δ

Associating High Oxide-Ion Conductivity and Conduction Mechanisms with Local Atomic Environments in Na_0.5Bi_0.5–xTi_1–yMg_yO_3−δ

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NMR investigations unveil phase composition–property correlations in Sr0.55Na0.45SiO2.775 fast ion conductor

Cited by 4 publications

References 33 publications

High Na+ conducting Na3Zr2Si2PO12/Na2Si2O5 composites as solid electrolytes for Na+ batteries

High Na+ conducting Na3Zr2Si2PO12/Na2Si2O5 composites as solid electrolytes for Na+ batteries

Electrochemical and degradation study of Sr0.6Na0.4SiO3-δ

Associating High Oxide-Ion Conductivity and Conduction Mechanisms with Local Atomic Environments in Na0.5Bi0.5–xTi1–yMgyO3−δ

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High Na⁺ conducting Na₃Zr₂Si₂PO₁₂/Na₂Si₂O₅ composites as solid electrolytes for Na⁺ batteries

High Na⁺ conducting Na₃Zr₂Si₂PO₁₂/Na₂Si₂O₅ composites as solid electrolytes for Na⁺ batteries

Associating High Oxide-Ion Conductivity and Conduction Mechanisms with Local Atomic Environments in Na_0.5Bi_0.5–xTi_1–yMg_yO_3−δ