Understanding the sodium-ion dynamics in NASICON (Na3Al2P3O12) glass containing NaF: Scaling of electrical conductivity spectra

Mandal, Indrajeet; Chakraborty, Saswata; Annapurna, K.; Sharma, Abhijit; Mukhopadhyay, Jayanta; Allu, Amarnath R.

doi:10.1016/j.jallcom.2021.160952

Cited by 15 publications

(17 citation statements)

References 63 publications

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“…The deconvolution results are provided in Table 2. Previous studies on similar types of glass suggest that the high-intensity vibrational band around 1030 cm −1 is due to the symmetric stretching vibrations of P-O − bonds located in AlPO 4 groups, which are enriched with Q 0 (3Al) and Q 0 (2Al) units in NAP glass (Mandal et al, 2021). However, as it has been reported by Yifen et al (Yifen et al, 1986), NAP glass consists of two types of AlPO 4 groups (AlPO4) 0 and (AlPO4) Na .…”

Section: Results and Discussion Ramanmentioning

confidence: 91%

“…Therefore, it can be confirmed that Sulphur exists in the form of sulfate in the NAP glass and occurs in the deep channel regions of NAP glass. In a previous report, it has been shown that the NAP glass network structure adopts the modified random network (MRN) model (Mandal et al, 2021). According to MRN model, the glass network structure consists of well-defined network regions separated by modifier cations enriched channel regions.…”

Section: Results and Discussion Ramanmentioning

confidence: 99%

“…In general, glass materials are treated as weak electrolyte materials since the ion conductivity in glass materials is largely dependent on the concentration of charge carriers instead of the mobility of mobile cations (Ingram et al, 1980). Considering this, many attempts have been made to increase the conductivity by increasing the concentration of mobile ions (Adhwaryu and Kanchan, 2021;Mandal et al, 2021). Nonetheless, this concept has not been fulfilled in many glass materials.…”

Section: Introductionmentioning

confidence: 99%

“…Several studies have reported that the conductivity of glass materials depends on the chemical composition-dependent network structure and the distribution of structural units around the alkali ions (Na + , Li + , etc.) (Jamal et al, 1999;Bhide and Hariharan, 2007;Mandal et al, 2021). Therefore, it is clearly understood that the factors governing the enhanced ionic conductivity in glass materials absolutely depend on the concentration, mobility, and on network structure of glass.…”

Section: Introductionmentioning

confidence: 99%

“…For example, H.Y-P. Hong (Hong, 1976) has reported that NASICON type Na 1+X Zr 2 Si X P 3-X O 12 crystal structure has faster ion conduction due to its skeleton structure consisting of a three-dimensional network. Recently, NASICON based Na 3 Al 2 P 3 O 12 (NAP) glass is studied for its structure and electrical properties and found that the conductivity can be enhanced by modifying its chemical compositions (Keshri et al, 2021;Mandal et al, 2021). NAP glass is mainly composed of PO 4 and AlO 4 tetrahedral units, where each PO 4 unit is surrounded by AlO 4 units.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Results and Discussion Ramanmentioning

confidence: 91%

Section: Results and Discussion Ramanmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2022

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Genome Mining in Glass Chemistry Using Linear Component Analysis of Ion Conductivity Data

2023

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Understanding the multivariate origin of physical properties is particularly complex for polyionic glasses. As a concept, the term genome has been used to describe the entirety of structure‐property relations in solid materials, based on functional genes acting as descriptors for a particular property, for example, for input in regression analysis or other machine‐learning tools. Here, the genes of ionic conductivity in polyionic sodium‐conducting glasses are presented as fictive chemical entities with a characteristic stoichiometry, derived from strong linear component analysis (SLCA) of a uniquely consistent dataset. SLCA is based on a twofold optimization problem that maximizes the quality of linear regression between a property (here: ionic conductivity) and champion candidates from all possible combinations of elements. Family trees and matrix rotation analysis are subsequently used to filter for essential elemental combinations, and from their characteristic mean composition, the essential genes. These genes reveal the intrinsic relationships within the multivariate input data. While they do not require a structural representation in real space, how possible structural interpretations agree with intuitive understanding of structural entities known from spectroscopic experiments is finally demonstrated.

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Amorphous Materials for Lithium‐Ion and Post‐Lithium‐Ion Batteries

Ding,

Ji,

Yue

et al. 2023

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Lithium‐ion and post‐lithium‐ion batteries are important components for building sustainable energy systems. They usually consist of a cathode, an anode, an electrolyte, and a separator. Recently, the use of solid‐state materials as electrolytes has received extensive attention. The solid‐state electrolyte materials (as well as the electrode materials) have traditionally been overwhelmingly crystalline materials, but amorphous (disordered) materials are gradually emerging as important alternatives because they can increase the number of ion storage sites and diffusion channels, enhance solid‐state ion diffusion, tolerate more severe volume changes, and improve reaction activity. To develop superior amorphous battery materials, researchers have conducted a variety of experiments and theoretical simulations. This review highlights the recent advances in using amorphous materials (AMs) for fabricating lithium‐ion and post‐lithium‐ion batteries, focusing on the correlation between material structure and properties (e.g., electrochemical, mechanical, chemical, and thermal ones). We review both the conventional and the emerging characterization methods for analyzing AMs and present the roles of disorder in influencing the performances of various batteries such as those based on lithium, sodium, potassium, and zinc. Finally, we describe the challenges and perspectives for commercializing rechargeable AMs‐based batteries.

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Understanding the sodium-ion dynamics in NASICON (Na3Al2P3O12) glass containing NaF: Scaling of electrical conductivity spectra

Cited by 15 publications

References 63 publications

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

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

Genome Mining in Glass Chemistry Using Linear Component Analysis of Ion Conductivity Data

Amorphous Materials for Lithium‐Ion and Post‐Lithium‐Ion Batteries

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