New Solid Electrolyte Na9Al(MoO4)6: Structure and Na+ Ion Conductivity

Savina, Aleksandra A.; Морозов, В.А.; Buzlukov, A. L.; Arapova, I. Yu.; Stefanovich, S. Yu.; Baklanova, Yana V.; Денисова, Т. А.; Medvedeva, N. I.; Bardet, Michel; Hadermann, Joke; Lazoryak, Bogdan I.; Хайкина, Е. Г.

doi:10.1021/acs.chemmater.7b03989

Cited by 35 publications

(22 citation statements)

References 79 publications

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“…For the recent years, complex molybdate crystals have become of extensive interest due to their stable chemical properties, rich crystal chemistry and potential applications in such fields as laser systems, electrochemistry and photonics [1][2][3][4][5][6][7][8][9][10]. Complex molybdates are actively investigated as host materials for the creation of rare-earth doped phosphors appropriate for the use in lightemitting devices [1,2,[11][12][13][14][15].…”

Section: Introductionmentioning

confidence: 99%

Microwave sol-gel synthesis, microstructural and spectroscopic properties of scheelite-type ternary molybdate upconversion phosphor NaPbLa(MoO4)3:Er3+/Yb3+

Lim

Aleksandrovsky

Atuchin

et al. 2020

Journal of Alloys and Compounds

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New ternary molybdate NaPbLa(1-x-y)(MoO4)3:xEr 3+ ,yYb 3+ (x = y = 0, x = 0.05 and y = 0.35, 0.4, 0.45 and 0.5) phosphors were successfully fabricated by the MSG (microwave sol-gel) method, and the microstructural and spectroscopic properties were characterized. The crystal structure of NaPbLa(MoO4)3 (NPLM) was defined by Rietveld analysis in space group I41/a with unit cell parameters a = 5.3735(2) and c = 11.8668 (4) Å, V = 342.65(3) Å 3 , Z = 4 (RB = 6.64 %). The unit cell volume of NaPbLa(MoO4)3 (NPLM) was intermediate between those of NaLa(MoO4)2 and PbMoO4. Under the 980 nm excitation, upconverted yellowish-green emissions at transitions from 2 H11/2 and 4 S3/2 were observed. No concentration quenching in the subsystem of donor ions at the content up to 50 at.% and no cross-relaxation losses in the subsystem of acceptor ions at the concentrations as high as 5 at. % were verified. The individual chromaticity points for the NaPbLa(MoO4)3:Er 3+ ,Yb 3+ phosphors, corresponding to the equal-energy point in the standard CIE diagram, revealed yellowish-green emissions.

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Section: Introductionmentioning

confidence: 99%

Microwave sol-gel synthesis, microstructural and spectroscopic properties of scheelite-type ternary molybdate upconversion phosphor NaPbLa(MoO4)3:Er3+/Yb3+

Lim

Aleksandrovsky

Atuchin

et al. 2020

Journal of Alloys and Compounds

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“…This correspondence relationship between the signals of ss‐NMR and crystal structure is further confirmed in the following. The splitting peak in P2′ phase region is caused by the quadrupolar interaction possibly, which comes from the quadrupolar nucleus 23 Na in an asymmetrical local environment . After doping with Al 3+ , only P2 signals can be observed in the spectra, which reveals that Al 3+ doping can reduce the Mn 3+ Jahn–Teller centers, as well as rearrange the local structures to form P2 phases.…”

Section: Resultsmentioning

confidence: 97%

P2‐Na_0.67Al_xMn_1−xO₂: Cost‐Effective, Stable and High‐Rate Sodium Electrodes by Suppressing Phase Transitions and Enhancing Sodium Cation Mobility

et al. 2019

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Sodium layered P2‐stacking Na0.67MnO2 materials have shown great promise for sodium‐ion batteries. However, the undesired Jahn–Teller effect of the Mn4+/Mn3+ redox couple and multiple biphasic structural transitions during charge/discharge of the materials lead to anisotropic structure expansion and rapid capacity decay. Herein, by introducing abundant Al into the transition‐metal layers to decrease the number of Mn3+, we obtain the low cost pure P2‐type Na0.67AlxMn1−xO2 (x=0.05, 0.1 and 0.2) materials with high structural stability and promising performance. The Al‐doping effect on the long/short range structural evolutions and electrochemical performances is further investigated by combining in situ synchrotron XRD and solid‐state NMR techniques. Our results reveal that Al‐doping alleviates the phase transformations thus giving rise to better cycling life, and leads to a larger spacing of Na+ layer thus producing a remarkable rate capability of 96 mAh g‐1 at 1200 mA g‐1.

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“…The difference in the number of cations in structurally similar and sodium-ion conducting Na 9 R(MoO 4 ) 6 (R = Fe, Al, Sc, In, Cr) (Savina et al, 2013b(Savina et al, ,b, 2017Dridi et al, 2015) compared with the title triple molybdates in that the X1 and M3 positions are fully occupied by sodium ions, while the M1 site at 3 is vacant. Thus, the framework of MoO 4 tetrahedra, octahedral M2(M3) 3 O 18 clusters and M1O 6 octahedra is divided into separate clusters [R 3+ (MoO 4 ) 6 ] 9À , and the space between them is filled by sodium ions.…”

Section: Crystal Chemistry Of the Ii-na 3 Fe 2 (Aso 4 ) 3 Familymentioning

confidence: 99%

“…The double molybdates Li 2 Co 2 (MoO 4 ) 3 (Prabaharan et al, 2004) and Li 3 V(MoO 4 ) 3 (Mikhailova et al, 2010) are isostructural with lyonsite, -Cu 3 Fe 4 (VO 4 ) 6 (Hughes et al, 1987), and are also of interest as cathode materials for rechargeable batteries. A prospective group of sodium-ion conductors may be Na 9 R(MoO 4 ) 6 (R = Fe, Al, Sc, In, Cr) (Savina et al, 2013a(Savina et al, ,b, 2017Dridi et al, 2015), the members of which, with iron and aluminium, show = 6.8 Â 10 À2 S cm À1 at 527 C (Savina et al, 2013b) and 1.63 Â 10 À2 S cm À1 at 530 C (Savina et al, 2017), respectively. The superionic high-temperature forms of these compounds seem to be isostructural with the high-temperature rhombohedral form of II-Na 3 Fe 2 (AsO 4 ) 3 (d' Yvoire et al, 1986Yvoire et al, , 1988, whose ionic conductivity reaches 8.3 Â 10 À4 S cm À1 at 300 C (d' Yvoire et al, 1986).…”

Section: Introductionmentioning

confidence: 99%

Triple molybdates K_3–xNa_1+x M ₄(MoO₄)₆ (M = Ni, Mg, Co) and K_3+xLi_1–xMg₄(MoO₄)₆ isotypic with II-Na₃Fe₂(AsO₄)₃ and yurmarinite: synthesis, potassium disorder, crystal chemistry and ionic conductivity

Gulyaeva

Солодовникова

Солодовников

et al. 2020

Acta Crystallogr Sect B

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The triple molybdates K3–x Na1+x M 4(MoO4)6 (M = Ni, Mg, Co) and K3+x Li1–x Mg4(MoO4)6 were found upon studying the corresponding ternary molybdate systems, and their structures, thermal stability and electrical conductiviplusmnty were investigated. The compounds crystallize in the space group R 3 c and are isostructural with the sodium-ion conductor II-Na3Fe2(AsO4)3 and yurmarinite, Na7(Fe3+, Mg, Cu)4(AsO4)6; their basic structural units are flat polyhedral clusters of the central M1O6 octahedron sharing edges with three surrounding M2O6 octahedra, which combine with single NaO6 octahedra and bridging MoO4 tetrahedra to form open three-dimensional (3D) frameworks where the cavities are partially occupied by disordered potassium (sodium) ions. The split alkali-ion positions in K3–x Na1+x M 4(MoO4)6 (M = Ni, Mg, Co) give their structural formulae as [(K,Na)0.5□0.5)]6(Na)[M1][M2]3(MoO4)6, whereas the lithium-containing compound (K0.5□0.5)6(Mg0.89K0.11)(Li0.89Mg0.11)Mg3(MoO4)6 shows an unexpected (Mg, K) isomorphism, which is similar to (Mn, K) and (Co, K) substitutions in isostructural K3+x Li1–x M 4(MoO4)6 (M = Mn, Co). The crystal chemistry of the title compounds and related arsenates, phosphates and molybdates was considered, and the connections of the cationic distributions with potential 3D ionic conductivity were shown by means of calculating the bond valence sum (BVS) maps for the Na+, Li+ and K+ ions. Electrical conductivity measurements gave relatively low values for the triple molybdates [σ = 4.8 × 10−6 S cm−1 at 390°C for K3NaCo4(MoO4)6 and 5 × 10−7 S cm−1 at 400°C for K3LiMg4(MoO4)6] compared with II-Na3Fe2(AsO4)3 (σ = 8.3 × 10−4 S cm−1 at 300°C). This may be explained by a low concentration of sodium or lithium ions and the blocking of their transport by large potassium ions.

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New Solid Electrolyte Na₉Al(MoO₄)₆: Structure and Na⁺ Ion Conductivity

Cited by 35 publications

References 79 publications

Microwave sol-gel synthesis, microstructural and spectroscopic properties of scheelite-type ternary molybdate upconversion phosphor NaPbLa(MoO4)3:Er3+/Yb3+

Microwave sol-gel synthesis, microstructural and spectroscopic properties of scheelite-type ternary molybdate upconversion phosphor NaPbLa(MoO4)3:Er3+/Yb3+

P2‐Na_0.67Al_xMn_1−xO₂: Cost‐Effective, Stable and High‐Rate Sodium Electrodes by Suppressing Phase Transitions and Enhancing Sodium Cation Mobility

Triple molybdates K_3–xNa_1+x M ₄(MoO₄)₆ (M = Ni, Mg, Co) and K_3+xLi_1–xMg₄(MoO₄)₆ isotypic with II-Na₃Fe₂(AsO₄)₃ and yurmarinite: synthesis, potassium disorder, crystal chemistry and ionic conductivity

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New Solid Electrolyte Na9Al(MoO4)6: Structure and Na+ Ion Conductivity

Cited by 35 publications

References 79 publications

Microwave sol-gel synthesis, microstructural and spectroscopic properties of scheelite-type ternary molybdate upconversion phosphor NaPbLa(MoO4)3:Er3+/Yb3+

Microwave sol-gel synthesis, microstructural and spectroscopic properties of scheelite-type ternary molybdate upconversion phosphor NaPbLa(MoO4)3:Er3+/Yb3+

P2‐Na0.67AlxMn1−xO2: Cost‐Effective, Stable and High‐Rate Sodium Electrodes by Suppressing Phase Transitions and Enhancing Sodium Cation Mobility

Triple molybdates K3–x Na1+x M 4(MoO4)6 (M = Ni, Mg, Co) and K3+x Li1–x Mg4(MoO4)6 isotypic with II-Na3Fe2(AsO4)3 and yurmarinite: synthesis, potassium disorder, crystal chemistry and ionic conductivity

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New Solid Electrolyte Na₉Al(MoO₄)₆: Structure and Na⁺ Ion Conductivity

P2‐Na_0.67Al_xMn_1−xO₂: Cost‐Effective, Stable and High‐Rate Sodium Electrodes by Suppressing Phase Transitions and Enhancing Sodium Cation Mobility

Triple molybdates K_3–xNa_1+x M ₄(MoO₄)₆ (M = Ni, Mg, Co) and K_3+xLi_1–xMg₄(MoO₄)₆ isotypic with II-Na₃Fe₂(AsO₄)₃ and yurmarinite: synthesis, potassium disorder, crystal chemistry and ionic conductivity