Influence of water on the electrochemical response of a bonded nasicon protonic conductor

Gulens, J.; Hildebrandt, B.W.; Canaday, J.D.; Kuriakose, A.K.; Wheat, T. A.; Ahmad, Aftab

doi:10.1016/0167-2738(89)90010-6

Cited by 25 publications

(7 citation statements)

References 6 publications

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“…With a sintering temperature of 350 °C, an additional phase appears with peaks adjacent to the primary R3̅c powder peaks but does not correspond to any reported structure within the sodium zirconium silicon phosphate solid-solution spectrum and does not correspond to any reported structure of crystalline NaOH . However, the secondary phase matches closely with the structure of rhombohedral (H 3 O)Zr 2 (PO 4 ) 3 ((H 3 O)ZP), where all (or at least a large fraction) of the sodium ions have been exchanged for hydronium ions (H 3 O + ) in an acidic medium − over the course of several days. The density and conductivity of these pellets are low, but it is notable that we were able to consistently produce this ion-exchange reaction concurrent with FH-CSP and tune the degree of reaction progression by varying the dwell time and w/w NaOH.…”

Section: Resultsmentioning

confidence: 88%

Densification of a Solid-State NASICON Sodium-Ion Electrolyte Below 400 °C by Cold Sintering With a Fused Hydroxide Solvent

Grady

Tsuji

Ndayishimiye

et al. 2020

ACS Appl. Energy Mater.

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A modified cold sintering process is described, which permits the densification of the prototypical sodium-ion electrolyte, Na 3 Zr 2 Si 2 PO 12 , to greater than 90% relative density at a process temperature below 400 °C. The roomtemperature grain boundary ionic conductivity is greater than 2 × 10 −4 S/cm. Sintering of Na 3 Zr 2 Si 2 PO 12 to such densities and conductivities typically requires sintering near 1200 °C for many hours. We modify the cold sintering process by replacing the aqueous transient solvent with a fused hydroxide (NaOH, T m = 312 °C) to increase the reactivity of the solvent−particle interaction while also retaining the increased driving forces for densification characteristic of cold sintering, namely, the transient nature of the solvent and uniaxial pressure applied to an open system. We demonstrate the changes in phase purity, conductivity, and density by varying the process temperature, weight fraction hydroxide, and dwell time. The best results are obtained near 375 °C, 10 w/w NaOH, and 3 h of sintering.

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Section: Resultsmentioning

confidence: 88%

Densification of a Solid-State NASICON Sodium-Ion Electrolyte Below 400 °C by Cold Sintering With a Fused Hydroxide Solvent

Grady

Tsuji

Ndayishimiye

et al. 2020

ACS Appl. Energy Mater.

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“…However, there are some arguments about the determination of bulk and grain-boundary resistance ( R b and R gb ). Several reports directly attribute R0 and R1 in the similar Nyquist plots to R b and R gb , respectively. ,− Thus, σ b can be derived from R0, as shown in Table . Although some others argue that the splitting between R b and R gb by R0 and R1 is not reliable because the high-frequency semicircle representing R b cannot be clearly seen in the Nyquist plots, , in the present study, the end part of the high-frequency semicircle representing R b separating from low-frequency semicircle representing R gb can be defined, indicating the reasonableness of the above analysis for Figure b.…”

Section: Resultsmentioning

confidence: 99%

Scandium-Substituted Na₃Zr₂(SiO₄)₂(PO₄) Prepared by a Solution-Assisted Solid-State Reaction Method as Sodium-Ion Conductors

et al. 2016

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As possible electrolyte materials for all-solid-state Na-ion batteries (NIBs), scandium-substituted Na 3 Zr 2 (SiO 4 ) 2 (PO 4 ) in the structure of NASICONs (Na super-ionic conductors) have received hardly any attention so far, although among all the trivalent cations, Sc 3+ might be the most suitable substitution ion for Na 3 Zr 2 (SiO 4 ) 2 (PO 4 ) because the ionic radius of Sc 3+ (74.5 pm) is the closest to that of Zr 4+ (72.0 pm). In this study, a solution-assisted solid-state reaction (SASSR) method is described and a series of scandium-substituted Na 3 Zr 2 (SiO 4 ) 2 (PO 4 ) with the formula of Na 3+x Sc x Zr 2-x (SiO 4 ) 2 (PO 4 ) (NSZSPx, 0 ≤ x ≤ 0.6) have been prepared. This synthesis route can be applied for powder preparation on a large scale and at low cost. With increasing degrees of scandium substitution, the total conductivity of the samples also increases. An optimum total Na-ion conductivity of 4.0 × 10 -3 S cm -1 at 25 °C is achieved by Na 3.4 Sc 0.4 Zr 1.6 (SiO 4 ) 2 (PO 4 ) (NSZSP0.4), which is the best value of all reported polycrystalline Na-ion conductors. The possible reasons for such high conductivity are discussed.

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“…It is quite common to discuss the conductivity of NASICON materials by Nyquist plots. 20,21,[26][27][28][29][30][31][32] However, limited by the frequency range of common impedance spectroscopy systems (up to 20 MHz), they usually show only one (or even half of one) semicircle in the plots at room temperature. Therefore, it is difficult to separate Rb and Rgb contributions.…”

Section: Properties Of the Sintered Samplesmentioning

confidence: 99%

Room temperature demonstration of a sodium superionic conductor with grain conductivity in excess of 0.01 S cm⁻¹ and its primary applications in symmetric battery cells

et al. 2019

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Influence of water on the electrochemical response of a bonded nasicon protonic conductor

Cited by 25 publications

References 6 publications

Densification of a Solid-State NASICON Sodium-Ion Electrolyte Below 400 °C by Cold Sintering With a Fused Hydroxide Solvent

Densification of a Solid-State NASICON Sodium-Ion Electrolyte Below 400 °C by Cold Sintering With a Fused Hydroxide Solvent

Scandium-Substituted Na₃Zr₂(SiO₄)₂(PO₄) Prepared by a Solution-Assisted Solid-State Reaction Method as Sodium-Ion Conductors

Room temperature demonstration of a sodium superionic conductor with grain conductivity in excess of 0.01 S cm⁻¹ and its primary applications in symmetric battery cells

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Influence of water on the electrochemical response of a bonded nasicon protonic conductor

Cited by 25 publications

References 6 publications

Densification of a Solid-State NASICON Sodium-Ion Electrolyte Below 400 °C by Cold Sintering With a Fused Hydroxide Solvent

Densification of a Solid-State NASICON Sodium-Ion Electrolyte Below 400 °C by Cold Sintering With a Fused Hydroxide Solvent

Scandium-Substituted Na3Zr2(SiO4)2(PO4) Prepared by a Solution-Assisted Solid-State Reaction Method as Sodium-Ion Conductors

Room temperature demonstration of a sodium superionic conductor with grain conductivity in excess of 0.01 S cm−1 and its primary applications in symmetric battery cells

Contact Info

Product

Resources

About

Scandium-Substituted Na₃Zr₂(SiO₄)₂(PO₄) Prepared by a Solution-Assisted Solid-State Reaction Method as Sodium-Ion Conductors

Room temperature demonstration of a sodium superionic conductor with grain conductivity in excess of 0.01 S cm⁻¹ and its primary applications in symmetric battery cells