NASICON solid electrolytes part I: The Na+-diffusion path and its relation to the structure

Kohler, Heinz; Schulz, H.

doi:10.1016/0025-5408(85)90164-3

Cited by 102 publications

(73 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Tran Qui et al 14 analyzing the size of the bottlenecks for ionic motion along these two paths concluded that Na(2)-Na(2) hops are more probable than Na(1)-Na(2) hops as the bottleneck for the Na(2)-Na(2) was found to be wider (and possibly offers a lower barrier). In contrast, Kohler and Shulz 11,13 analyzing the density distribution of Na + along the two paths suggested Na(1)-Na (2) hops are more probable than Na(2)-Na(2) hops. Mazza, 16 on the basis of bond valence equations also suggested that it is Na(1)-Na(2) hops that are more probable.…”

Section: Resultsmentioning

confidence: 93%

See 1 more Smart Citation

Structure, Conductivity, and Ionic Motion in Na₁₊_xZr₂Si_xP₃_-_xO₁₂: A Simulation Study

Kumar

Yashonath

2002

J. Phys. Chem. B

View full text Add to dashboard Cite

Constant-pressure, constant-temperature variable-shape simulation cell Monte Carlo and microcanonical ensemble molecular dynamics simulation of superionic conducting rhombohedral phase of Nasicon, Na 1+x Zr 2 Si x P 3-x O 12 , 0 e x e 3, at a temperature of 600 K is reported. Changes in structure, conductivity, hop path, site occupancies, bond lengths of framework atoms with composition are discussed. Average Na(1)-O distance shows a peak at x ) 2, while Na(2)-O distance shows a monotonic increase. Sum of the sodium occupancies at Na(1) and mid-Na sites adds up to a constant value of one which supports the conclusion of Boilot et al. 1 based on X-ray diffraction. Occupancy of Na(1) site attains a minimum at x ) 2. The predominant conduction channel (which carries more than 90% of the sodium ions) is found to be the one connecting Na(1)-mid-Na-Na(2). Density contours for sodium, depicting this conduction channel, are reported. Free energy profile along the conduction channel suggests that entropy contribution cannot be neglected. The mid-Na site is not associated with a free energy minimum.

show abstract

Section: Resultsmentioning

confidence: 93%

“…Different groups have suggested different pathways for Na + migration. 11,13,14 Even after numerous experimental investigations, in the past three decades, many aspects of the ionic motion in these materials remain poorly understood.…”

Section: Introductionmentioning

confidence: 99%

Structure, Conductivity, and Ionic Motion in Na₁₊_xZr₂Si_xP₃_-_xO₁₂: A Simulation Study

Kumar

Yashonath

2002

J. Phys. Chem. B

View full text Add to dashboard Cite

show abstract

“…On the basis of a random distribution of tri-and tetravalent cations, five possible environments for P atoms can be envisaged in the Na 1.4 Al 0.4 M 1.6 (PO 4 ) 3 phases: P(OM) 4 , P(OM) 3 (OAl), P(OM) 2 (OAl) 2 , P(OM)(OAl) 3 and P(OAl) 4 . From statistical considerations [17], the highest detected component must correspond to the first environment, P(OM) 4 . The variation observed in the position of the P(OM) 4 ''main'' signal in the five samples is associated with differences in the polarizing strength of the tetravalent cation, see Table 5.…”

Section: P Mas-nmr Studymentioning

confidence: 99%

Nominal vs. actual stoichiometries in Al-doped NASICONs: A study of the Na1.4Al0.4M1.6(PO4)3 (M=Ge, Sn, Ti, Hf, Zr) family

et al. 2005

View full text Add to dashboard Cite

“…the metal-oxygen polyhedra occupied by charge carriers should be connected in one (tunnel structures), two (layered structures) or, most preferable, three dimensions forming a pathway through the unit cell. One of the best groups of sodium ion conductors, so-called NASICONs, is characterized by a threedimensional conductivity path [5]; β-alumina has a layered structure [6]. Another family of layered compounds, having cationic conductivity comparable to those of NASICONs, comprises several structural types based on brucite-like octahedral layers MO 6/3 (where M is transition metal) sandwiching alkali cations between them [7][8][9][10][11].…”

Section: Introductionmentioning

confidence: 99%

Síntesis y caracterización del conductor catiónico de sodio Nax(MyL1-y)O2 (M = Ni2+, Fe3+; L = Ti4+, Sb5+)

Smirnova¹,

Хартон²,

Marques³

2004

Bol. Soc. Esp. Ceram. Vidr.

View full text Add to dashboard Cite

The Na + -conducting ceramics of layered Na 0.8 Ni 0.4 Ti 0.6 O 2 , Na 0.8 Fe 0.8 Ti 0.2 O 2 , Na 0.8 Ni 0.6 Sb 0.4 O 2 (structural type O3) and Na 0.68 Ni 0.34 Ti 0.66 O 2 (P2 type) with density higher than 91% were prepared via the standard solid-state synthesis route and characterized by the impedance spectroscopy, thermal analysis, scanning electron microscopy, structure refinement using X-ray powder diffraction data, measurements of Na + concentration cell e.m.f., and dilatometry. The conductivity of antimonate Na 0.8 Ni 0.6 Sb 0.4 O 2 , synthesized first time, was found lower than that of isostructural Na 0.8 Ni 0.4 Ti 0.6 O 2 due to larger ion jump distance between Na + sites. At temperatures above 420 K, transport properties of sodium cationconducting materials are essentially independent of partial water vapor pressure. In the low-temperature range, the conductivity reversibly increases with water vapor pressure varied in the range from approximately 0 (dry air) up to 0.46 atm. The sensitivity to air humidity is influenced by the ceramic microstructure, being favored by increasing boundary area. The average thermal expansion coefficients of layered materials at 300-1173 K are in the range (13.7-16.0)×10 (tipo P2) con densidad mayor del 91%. Las vía de preparación fu la ruta de estandard de síntesis en estado sólido. Las composiciones se caracterizaron mediante espectroscopía de impedancia, análisis térmico, microscopía electrónica de barrido, refinamiento de la estructura usando datos de difracción de rayos X en polvo, medidas de concentración de Na + , f.e.m. de la célula y dilatometría. La conductividad del antimoniate, sintetizado por primera vez, Na 0.8 Ni 0.6 Sb 0.4 O 2 , era menor que la del compuesto isoestructural Na 0.8 Ni 0.4 Ti 0.6 O 2 debido a la mayor distancia de salto iónico entre las posiciones de Na + . A temperaturas por encima de 420 K, las propiedades de transporte de los materiales conductores que contienen cations sodio son esencialmente independientes de la presión parcial de vapor de agua. En el intervalo de baja temperatura, la conductividad aumenta reversiblemente con la presión de vapor de agua variando en un intervalo de aproximadamente 0 (aire seco) hasta 0.46 atm. La sensibilidad a la humedad del aire está influída por la microestructura de la cerámica, estando favorecida al aumentar el área de borde. Los coeficientes de dilatación térmica medios de los materiales laminares entre 300 y 1173 K están en el intervalo (13.7-16.0)×10 -6 K -1 .Palabras clave: conductor con cationes sodio, espectroscopia de impedancia, humedad del aire, dilatación térmica, microestructura cerámica.

show abstract

NASICON solid electrolytes part I: The Na+-diffusion path and its relation to the structure

Cited by 102 publications

References 14 publications

Structure, Conductivity, and Ionic Motion in Na₁₊_xZr₂Si_xP₃_-_xO₁₂: A Simulation Study

Structure, Conductivity, and Ionic Motion in Na₁₊_xZr₂Si_xP₃_-_xO₁₂: A Simulation Study

Nominal vs. actual stoichiometries in Al-doped NASICONs: A study of the Na1.4Al0.4M1.6(PO4)3 (M=Ge, Sn, Ti, Hf, Zr) family

Síntesis y caracterización del conductor catiónico de sodio Na<sub>x</sub>(M<sub>y</sub>L<sub>1-y</sub>)O<sub>2</sub> (M = Ni<sup>2+</sup>, Fe<sup>3+</sup>; L = Ti<sup>4+</sup>, Sb<sup>5+</sup>)

Contact Info

Product

Resources

About

NASICON solid electrolytes part I: The Na+-diffusion path and its relation to the structure

Cited by 102 publications

References 14 publications

Structure, Conductivity, and Ionic Motion in Na1+xZr2SixP3-xO12: A Simulation Study

Structure, Conductivity, and Ionic Motion in Na1+xZr2SixP3-xO12: A Simulation Study

Nominal vs. actual stoichiometries in Al-doped NASICONs: A study of the Na1.4Al0.4M1.6(PO4)3 (M=Ge, Sn, Ti, Hf, Zr) family

Síntesis y caracterización del conductor catiónico de sodio Na<sub>x</sub>(M<sub>y</sub>L<sub>1-y</sub>)O<sub>2</sub> (M = Ni<sup>2+</sup>, Fe<sup>3+</sup>; L = Ti<sup>4+</sup>, Sb<sup>5+</sup>)

Contact Info

Product

Resources

About

Structure, Conductivity, and Ionic Motion in Na₁₊_xZr₂Si_xP₃_-_xO₁₂: A Simulation Study

Structure, Conductivity, and Ionic Motion in Na₁₊_xZr₂Si_xP₃_-_xO₁₂: A Simulation Study