Electrical properties and scaling studies of Na3+x ZrxSc2−x(PO4)3 glass ceramic electrolyte for use in Na-ion batteries

Gandi, Shyam Sundar; Gandi, Suman; Katari, Naresh Kumar; Dutta, Dimple P.; Ravuri, Balaji Rao

doi:10.1007/s00339-019-2392-4

Cited by 9 publications

(3 citation statements)

References 24 publications

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“…The Li 1+ x Al x Ge 2– x (PO 4 ) 3 , Li 1+ x In x Hf 2– x (PO 4 ) 3 , and Li 1+ x Al x Ti 2– x (PO 4 ) 3 series are common examples. ,,, However, even more complex compositions can be planned. Phosphorus can be partially replaced by silicon, as an example of the Na 1+ x Zr 2 P 3– x Si x O 12 compoundone of the first explored Na + super conductors. ,− Structural inclusions of alkaline-earth elements such as magnesium, Li 1.6 Mg 0.3 Ti 1.7 (PO 4 ) 3 , or even total substitution of B (IV) cation to vanadium, Li 3 V 2 (PO 4 ) 3 , are also possible. ,,,− Therefore, a more complete formula for NASICON compounds lies in the A (I) 1+2 v + w – x + y ·M (II) v M (III) w M (V) x M (IV) 2– v – w – x (SiO 4 ) y F z (PO 4 ) 3– y − z general stoichiometry …”

Section: General Aspects Of Nasicon Structurementioning

confidence: 99%

Methods for Lithium Ion NASICON Preparation: From Solid-State Synthesis to Highly Conductive Glass-Ceramics

2020

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Lithium ion-containing Na + Super Ionic Conductor (NASICON) electrolytes are important materials for new energystorage technologies. The NASICON abbreviation represents several compounds with similar structures applied as solid electrolytes, including those conductors of lithium ions. Different methods have been used to synthesize these materials, as well as innumerous other methods used to form the electrolyte in its final shape. The synthesis methods and processing techniques significantly affect the microstructure and conductivity of the electrolyte as a result. Therefore, this paper provides an overview of the main synthesis methods and processing techniques applied for lithium ion NASICON production. First, a general view of the NASICON structure and the variety of possible compositions will be discussed. Next, the influence of the synthesis methods (e.g., solid-state reaction, sol−gel, polymeric precursor, sol−gel/ electrospinning) and sintering techniques (e.g., conventional, microwave, and Spark Plasma Sintering) will be presented. A special topic will be devoted for glass-ceramics production and evaluation, based on their advantageous ionic conductivity and potentiality for practical use on a large-scale. Moreover, the current results for electrochemical cells simulating the application of these materials in batteries will be presented. Finally, a general point of view of the authors about the future for NASICON electrolytes will be provided, presenting oncoming trends for research.

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Section: General Aspects Of Nasicon Structurementioning

confidence: 99%

Methods for Lithium Ion NASICON Preparation: From Solid-State Synthesis to Highly Conductive Glass-Ceramics

2020

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“…This result confirms the sharp enhancement in conductivity with respect to temperature rise as inferred from temperature-dependent conductivity analysis. [38,39]…”

Section: Ac Impedance Analysis and Nyquist Plotsmentioning

confidence: 99%

Development of high‐performance biopolymer nanocomposites derived from carboxymethyl chitosan/boehmite via green synthesis

Meera

Ramesan

2022

Polymer Composites

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In this work, biopolymer nanocomposites derived from carboxymethyl chitosan (CMCS) and boehmite were prepared via an environmentally friendly technique and their structural, morphological, thermal, electrical, dielectric, and mechanical properties were investigated. The successful fabrication of carboxymethyl chitosan/boehmite nanocomposites was evident from the appearance of characteristic peaks of boehmite in FTIR and alteration in the morphology as revealed by optical and SEM micrographs. The glass transition temperature (T g ) and melting temperature (T m ) were increased as the filler content increased. The enhanced thermal stability of nanocomposites was clear from thermogravimetric results. The incorporation of boehmite nanoparticles into CMCS improved the conductivity to a semiconducting range. The dielectric constant of CMCS/boehmite nanocomposites was significantly higher compared to pure CMCS. The influence of temperature on AC conductivity, activation energy, dielectric constant and loss tangent were analyzed. Complex impedance analysis carried out by Nyquist plots and the bulk resistance showed a decreasing trend with temperature, which indicated enhanced conductivity with temperature. Tensile strength and hardness were observed to be increased with boehmite inclusion, whereas elongation at break is reduced. As a result, eco-friendly CMCS/boehmite biopolymer nanocomposites with good thermal, mechanical, electric, and dielectric properties may be a potential green alternative for flexible electronic, charge storage, and other electrochemical devices.

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“…In the search for good candidates for solid-state electrolytes, Na + super ionic conductor (NASICON) compounds have been gaining ground since 1976 for this use . They are phosphate-type compounds with the basic-A (I) B 2 (IV) (PO 4 ) 3 stoichiometry, in which: (1) A (I) is a monovalent mobile cation (e.g., Li + , − Na + , − Ag + ) and (2) B (IV) an octahedrally coordinated cation, surrounded by oxygen anions (e.g., Zr 4+ , , Ti 4+ , , Ge 4+ , − Hf 4+ , ). Thus, lithium-ion NASICONs utilize Li + as the mobile cation in the compound’s structure.…”

Section: Introductionmentioning

confidence: 99%

Understanding the Evolution of the Structure and Electrical Properties during Crystallization of Li_1.5Al_0.5Ge_1.5(PO₄)₃ and Li_1.5Sc_0.17Al_0.33Ge_1.5(PO₄)₃ NASICON -Type Glass Ceramics

et al. 2023

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In this paper, the effects of crystallization advance on the material structure and electrical properties of lithium-ion Na+ super ionic conductor (NASICON) glass ceramics were investigated. Glasses with Li1.5Al0.5Ge1.5(PO4)3 and Li1.5Sc0.17Al0.33Ge1.5(PO4)3 compositions were crystallized in controlled conditions to obtain gradual increment of the volume crystallized fraction. The glass-to-crystal transformation was then monitored by differential scanning calorimetry analysis (DSC), X-ray diffractometry (XRD), Raman spectroscopy, solid-state nuclear magnetic resonance spectroscopy (MAS NMR), and electron microscopy, along with chemical analyses. Finally, the electrical properties of the specimens were evaluated by impedance spectroscopy to observe the changes in electrical properties according to the crystallization advance. Results revealed that glasses containing scandium are more stable against crystallization than their neat counterparts. Crystallization led to the formation of single-phase NASICON glass ceramics. Scandium induced a lattice expansion of the NASICON structure. Furthermore, crystallization induces remarkable structural changes in the materials as a whole, either in local order or in medium to long order. No important increase in conductivity was observed in earlier stages of crystallization. After the percolation of crystals, conductivity increases sharply and the remaining glassy phase has little impact on the total conductivity of the material. Scandium expands the rhombohedral structure but increases the glass stability and reduces the sizes of crystals for the fully crystallized glass ceramics. Glass ceramics with larger grains are more propitious for conductivity than the more refined ones. Therefore, this paper offers key information about the understanding of NASICON crystallization and its structural evolution, providing important insights into the crystallization of these electrolytes.

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Electrical properties and scaling studies of Na3+x ZrxSc2−x(PO4)3 glass ceramic electrolyte for use in Na-ion batteries

Cited by 9 publications

References 24 publications

Methods for Lithium Ion NASICON Preparation: From Solid-State Synthesis to Highly Conductive Glass-Ceramics

Methods for Lithium Ion NASICON Preparation: From Solid-State Synthesis to Highly Conductive Glass-Ceramics

Development of high‐performance biopolymer nanocomposites derived from carboxymethyl chitosan/boehmite via green synthesis

Understanding the Evolution of the Structure and Electrical Properties during Crystallization of Li_1.5Al_0.5Ge_1.5(PO₄)₃ and Li_1.5Sc_0.17Al_0.33Ge_1.5(PO₄)₃ NASICON -Type Glass Ceramics

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Electrical properties and scaling studies of Na3+x ZrxSc2−x(PO4)3 glass ceramic electrolyte for use in Na-ion batteries

Cited by 9 publications

References 24 publications

Methods for Lithium Ion NASICON Preparation: From Solid-State Synthesis to Highly Conductive Glass-Ceramics

Methods for Lithium Ion NASICON Preparation: From Solid-State Synthesis to Highly Conductive Glass-Ceramics

Development of high‐performance biopolymer nanocomposites derived from carboxymethyl chitosan/boehmite via green synthesis

Understanding the Evolution of the Structure and Electrical Properties during Crystallization of Li1.5Al0.5Ge1.5(PO4)3 and Li1.5Sc0.17Al0.33Ge1.5(PO4)3 NASICON -Type Glass Ceramics

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Understanding the Evolution of the Structure and Electrical Properties during Crystallization of Li_1.5Al_0.5Ge_1.5(PO₄)₃ and Li_1.5Sc_0.17Al_0.33Ge_1.5(PO₄)₃ NASICON -Type Glass Ceramics