Na3+x[CrxTi2-x(PO4)3] glass-ceramic electrolyte: ionic conductivity and structural correlations for different heat treating temperatures and time schedules

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

doi:10.1007/s11581-019-02979-6

Cited by 10 publications

(3 citation statements)

References 27 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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“…Vanadium bronze is predicted to be applied as an active cathode material for secondary batteries because it has high electrical conductivity (10 0 -10 1 S cm −1 ) [24] and high cycle stability [25]. In addition, the electrical conductivity of vanadium bronze is high compared with other compounds used as cathode material such as Na 4 ZrSi 4 O 12 (1.96 × 10 −4 S cm −1 ) [26], Na 3.5 Cr 0.5 Ti 1.5 (PO 4 ) 3 (8.5× 10 −4 S cm −1 ) [27], and Na 1.5 Al 0.5 Ge 1.5 P 3 O 12 (9.27× 10 −5 S cm −1 ) [28]. Kubuki et al reported…”

Section: Introductionmentioning

confidence: 99%

Structural, Electrical, and Electrochemical Properties of a Na2O-V2O5 Ceramic Nanocomposite as an Active Cathode Material for a Na-Ion Battery

Ibrahim,

Watanabe,

Razum

et al. 2023

Crystals

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In this paper, a relationship between the structure and the electrical properties of a nanocrystalline composite ceramics xNa2O·(100 − x)V2O5 with ‘x’ of 5, 15, 25, 35, and 45 mol%, abbreviated as xNV, was investigated by X-ray diffractometry (XRD), X-ray absorption spectroscopy (XAS), Cyclic Voltammetry (CV), Electrochemical impedance spectroscopy (EIS), and cathode active performance in Na-ion battery (SIB). For the expected sodium vanadium bronzes (NaxV2O5) precipitation, the preparation of xNV was performed by keeping the system in the molten state at 1200 °C for one hour, followed by a temperature decrease in the electric furnace to room temperature at a cooling rate of 10 °C min−1. XRD patterns of the 15NV ceramic exhibited the formation of Na0.33V2O5 and NaV3O8 crystalline phases. Moreover, the V K-edge XANES showed that the absorption edge energy of ceramics 15NV recorded at 5479 eV is smaller than that of V2O5 at 5481 eV, evidently indicating a partial reduction from V5+ to V4+ due to the precipitation of Na0.33V2O5. In the cyclic voltammetry, reduction peaks of 15NV were observed at 1.12, 1.78 V, and 2.69 V, while the oxidation peak showed up only at 2.36 V. The values of the reduction peaks were related to the NaV3O8 crystalline phase. Moreover, the diffusion coefficient of Na+ (DNa+) gradually decreased from 8.28 × 10−11 cm2 s−1 to 1.23 × 10−12 cm2 s−1 with increasing Na2O content (x) from 5 to 45 mol%. In the evaluation of the active cathode performance of xNV in SIB, ceramics 15NV showed the highest discharge capacity 203 mAh g−1 at a current rate of 50 mA g−1. In the wider voltage range from 0.8 to 3.6 V, the capacity retention was maintained at 50% after 30 cycles, while it was significantly improved to 90% in the narrower voltage range from 1.8 to 4.0 V, although the initial capacity decreased to 56 mAh g−1. It is concluded that the precipitation of the Na0.33V2O5 phase improved the structural and electrical properties of 15NV, which provides a high capacity for the Na-ion battery when incorporated as a cathode active material.

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“…Alternatively, solid-state sodium metal batteries employing solid-state electrolytes and sodium metal anodes can effectively solute the safety issues originating from organic liquid electrolytes and highly improve the energy density of devices [3,4]. In view of their excellent structural and chemical stability, high ionic conductivity (>10 −4 S cm −1 ) and wide electrochemical window (>5 V), NASICON-type solid electrolytes have received abundant research attention in recent years [5,6]. As a typical NASICON structure, Na 3 Zr 2 Si 2 PO 12 (NZSP) was firstly exploited in 1976 by Hong and Goodenough and reported widely owing to its relative higher ionic conductivity [7,8].…”

Section: Introductionmentioning

confidence: 99%

Bi2O3-Assisted Sintering of Na3Zr2Si2PO12 Electrolyte for Solid-State Sodium Metal Batteries

et al. 2022

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Solid-state sodium metal batteries using non-flammable solid-state electrolytes are recognized as next-generation energy storage technology in view of their merits of high safety and low cost. However, the lower ion conductivity (below the application requirements of 10−3 S cm−1) and interface issues that exist in electrolytes/electrodes for most solid-state electrolytes hinder their practical application. In this paper, NASICON-type Na3Zr2Si2PO12 (NZSP) electrolytes with enhanced ion conductivity are synthesized by the Bi2O3-assisted sintering method. The influence of the Bi2O3 sintering agent content on the crystalline phase, microstructure, density and ion conductivity as well as the electrochemical performances applied in batteries for the obtained NZSP electrolytes are investigated in detail. With the presence of Bi2O3, the formed Na3Bi(PO4)2 impurity increased the Si/P ratio in the NASICON structure with higher Na+ occupancy, then enhanced the ionic conductivity to a level of 1.27 × 10−3 S cm−1. Unfortunately, the Bi2O3-assisted sintered NZSP shows a degradation in the cycling stability when applied to solid-state sodium batteries because of the decreased interfacial stability with Na anodes. The formation of a Bi-Na alloy during cycling might be conducive to Na dendrite growth in electrolytes, degrading the cycling performance. This work presents a facial method to improve the ion conductivity of NASICON-type electrolytes and gives insight into the interface issues of solid-state sodium metal batteries.

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Na3+x[CrxTi2-x(PO4)3] glass-ceramic electrolyte: ionic conductivity and structural correlations for different heat treating temperatures and time schedules

Cited by 10 publications

References 27 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

Structural, Electrical, and Electrochemical Properties of a Na2O-V2O5 Ceramic Nanocomposite as an Active Cathode Material for a Na-Ion Battery

Bi2O3-Assisted Sintering of Na3Zr2Si2PO12 Electrolyte for Solid-State Sodium Metal Batteries

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