Nonstoichiometry in the systems Na2MoO4–MMoO4 (M = Co, Cd), crystal structures of Na3.36Co1.32(MoO4)3, Na3.13Mn1.43(MoO4)3 and Na3.72Cd1.14(MoO4)3, crystal chemistry, compositions and ionic conductivity of alluaudite-type double molybdates and tungstates

Солодовников, С. Ф.; Солодовникова, З. А.; Золотова, Е. С.; Yudin, Vasiliy N.; Gulyaeva, Oksana A.; Tushinova, Yunna L.; Kuchumov, B. M.

doi:10.1016/j.jssc.2017.05.031

Cited by 35 publications

(30 citation statements)

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“…A large number of double molybdates and tungstates of alkaline elements with di-or trivalent metals is an area of increasing interest because of the wide range of important physical properties and because of the potential applications of these compounds, such as promising optical materials (Maczka et al, 2012;Shimemura et al, 2017), effective phosphors (Benoît et al, 2011;Mo et al, 2012;Wang et al, 2009), laser materials (Balda et al, 2006;Yu et al, 2016;Loiko et al, 2016), as well as ferroelectrics (Isupov, 2005a,b) and solidstate electrolytes (Savina et al, 2013;Tsyrenova et al, 2016;Shukaev et al, 2016;Solodovnikov et al, 2017). Double molybdates and tungstates of two different alkali cations are also of special interest.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, crystal structures and properties of the new compounds K_7–xAg_1+x(XO₄)₄ (X = Mo, W)

Spiridonova

Солодовников

Savina

et al. 2017

Acta Crystallogr C Struct Chem

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Two new isostructural compounds, namely heptapotassium silver tetrakis(tetraoxomolybdate), KAg(MoO) (0 ≤ x ≤ 0.4), and heptapotassium silver tetrakis(tetraoxotungstate), KAg(WO) (0 ≤ x ≤ 0.4), have been synthesized and found to crystallize in the polar space group P6mc (Z = 2) with the unit-cell dimensions a = 12.4188 (2) and c = 7.4338 (2) Å for KAg(MoO) (single-crystal data), and a = 12.4912 (5) and c = 7.4526 (3) Å for KAg(WO) (Rietveld analysis data). Both structures represent a new structure type, with characteristic [K1(XO)] `pinwheels' of K1O octahedra and six XO tetrahedra (X = Mo, W) connected by common opposite faces into columns along the c axes. The octahedral columns are linked to each other through Ag1O tetrahedra along with the K2 and K3/Ag2 polyhedra, forming the polar rods (...Ag1O-X1O-empty octahedron-Ag1O...). Ag1 is located almost at the centre of the largest face of its coordination tetrahedron and seems to have some mobility. The new structure type is related to the BaNdAlO and CaBaSiO types, and to other structures of the α-KSO-glaserite family. The differential scanning calorimetry (DSC) and second harmonic generation (SHG) results show that both compounds undergo first-order phase transformations to high-temperature centrosymmetric phases.

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Section: Introductionmentioning

confidence: 99%

Synthesis, crystal structures and properties of the new compounds K_7–xAg_1+x(XO₄)₄ (X = Mo, W)

Spiridonova

Солодовников

Savina

et al. 2017

Acta Crystallogr C Struct Chem

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“…Na3 Na3 Согласно данным для Na 3.13 Mn 1.43 (MoO 4 ) 3 [18], заполнение позиции 8 f ионами марганца составляет 0.717 (и 0.280 -ионами натрия). Таким образом, из восьми f -позиций металла в элементарной ячейке примерно шесть заполнены марганцем и две -натрием.…”

Section: Na2unclassified

“…Позиция Na3 имеет заполнение 0.670 [16]. В молибдатах железа, кобальта и никеля заполнение металлом позиции 8 f составляет 1.0, 0.660 и 0.654 соот-ветственно, а степень заполнения позиции Na3 равна 1.0, 0.719 и 0.693 соответственно [18,43,44].…”

Section: Na2unclassified

Электронная структура и квадрупольные взаимодействия в перспективных катодных материалах Na-=SUB=-x-=/SUB=-M-=SUB=-y-=/SUB=-(MoO-=SUB=-4-=/SUB=-)-=SUB=-3-=/SUB=-, M=Mn, Fe, Co и Ni

Медведева¹,

Сердцев²

2019

Физика Твердого Тела

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The electronic structure and the magnetic properties of molybdates Na_ x M_ y (MoO_4)_3 (M = Mn, Fe, Co, and Ni) which are promising materials for sodium batteries have been studied in the framework of the density functional theory with the GGA and GGA+ U approximations for the first time. The calculations show that all the compounds are insulators. An important role of the correlation effects, provided by the on-site Coulomb interactions, was established in the formation of the band gap in these compounds. The quadrupole constants of ^23Na nuclei are calculated in the nonmagnetic and ferromagnetic states within the GGA and GGA+ U approaches. It is shown that the quadrupole frequencies for nonequivalent crystallographic positions of sodium are in different frequency ranges, which allows to study the diffusion of sodium in these compounds by the Nuclear Magnetic Resonance method.

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“…Orthophosphates and sulfates adopting the structure of alluaudite (Na, Ca)(Fe, Mn, Mg)(PO 4 ) 3 (space group C 2/ c, a = 12.004, b = 12.533, c = 6.404 Å, β = 114.4°, Z = 4) with open 3D frameworks and channels along the shortest c ‐axis and variable contents of sodium (lithium) and transition metal cations are considered as promising Na‐ or Li‐ion conductors or battery materials . The alluaudite‐type structure is also found for double molybdates Na 4–2 x M 1+ x (MoO 4 ) 3 ( M = Mg, Mn, Co, Ni, Cu, Zn, Cd; 0 ≤ x ≤ 0.50), K 4–2 x Cd 1+ x (MoO 4 ) 3 (0.14 ≤ x ≤ 0.38),[3d] Na 5 Sc(MoO 4 ) 4 , Na 5 In(MoO 4 ) 4 , β‐Na 9 Cr(MoO 4 ) 6 , as well as for triple molybdates K 0.4 Na 3.6 Co(MoO 4 ) 3 , KNa 5 Mn 3 (MoO 4 ) 6 , K 0.13 Na 3.87 Mg(MoO 4 ) 3 and double tungstates Na 4 Mg(WO 4 ) 3 and Na 5 Sc(WO 4 ) 4 . [3c] The crystal chemistry and compositions of the alluaudite‐type molybdates and tungstates was considered by us in.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Conductivity of Alluaudite‐Related Phases in the Na₂MoO₄–Cs₂MoO₄–CoMoO₄ System

et al. 2018

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Phase formation study of the Na2MoO4–Cs2MoO4–CoMoO4 system resulted in new cesium‐containing alluaudite‐related phases. The solid solution Na4–2x‐yCsyCo1+x(MoO4)3 (0 ≤ x, y ≤ 0.30), based on the alluaudite‐type Na4–2xCo1+x(MoO4)3, and triple molybdate Na10(Cs4‐xNax)Co5(MoO4)12 (0 ≤ x ≤ 0.30) were found, and their structures were solved. In the structure of Na3.21Cs0.37Co1.21(MoO4)3 (a = 13.0917(8) Å, b = 13.5443(8) Å, c = 7.1217(4) Å, space group C2/c, β = 112.331(2), Z = 4), the cesium ions partially substitute the Na+ in the channels running along the c‐axis. The structure of Na10(Cs3.77Na0.23)Co5(MoO4)12 (a = 13.6572(3) Å, b = 11.5063(3) Å, c = 27.9898(5) Å, space group Pbca, Z = 4) was proved to be the aristotype for the pseudo orthorhombic Na25Cs8R5(MoO4)24 (R = Fe, Sc, In). The compounds contain alluaudite‐like layers of MoO4 tetrahedra and pairs of edge‐shared (Co, Na)O6 or (R, Na)O6 and NaO6 octahedra, which are connected by bridging MoO4 tetrahedra to form 3D frameworks differing from the alluaudite type. The frameworks contain channels along the c‐axis filled by Cs+ and Na+ ions. Bond valence sum (BVS) maps show that the alluaudite‐related molybdates can have a 2D sodium‐ion conductivity at elevated temperatures in contrast to the alluaudite‐type cathode material Na2+2xFe2‐x(SO4)3 with a 1D conductivity. The measured ionic conductivity of Na4–2xCo1+x(MoO4)3, Na4–2x‐yCsyCo1+x(MoO4)3, and Na10Cs4Co5(MoO4)12 reaches 10–3–10–2 S cm–1 at 500 °C.

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Nonstoichiometry in the systems Na2MoO4–MMoO4 (M = Co, Cd), crystal structures of Na3.36Co1.32(MoO4)3, Na3.13Mn1.43(MoO4)3 and Na3.72Cd1.14(MoO4)3, crystal chemistry, compositions and ionic conductivity of alluaudite-type double molybdates and tungstates

Cited by 35 publications

References 31 publications

Synthesis, crystal structures and properties of the new compounds K_7–xAg_1+x(XO₄)₄ (X = Mo, W)

Synthesis, crystal structures and properties of the new compounds K_7–xAg_1+x(XO₄)₄ (X = Mo, W)

Электронная структура и квадрупольные взаимодействия в перспективных катодных материалах Na-=SUB=-x-=/SUB=-M-=SUB=-y-=/SUB=-(MoO-=SUB=-4-=/SUB=-)-=SUB=-3-=/SUB=-, M=Mn, Fe, Co и Ni

Synthesis, Structure, and Conductivity of Alluaudite‐Related Phases in the Na₂MoO₄–Cs₂MoO₄–CoMoO₄ System

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Nonstoichiometry in the systems Na2MoO4–MMoO4 (M = Co, Cd), crystal structures of Na3.36Co1.32(MoO4)3, Na3.13Mn1.43(MoO4)3 and Na3.72Cd1.14(MoO4)3, crystal chemistry, compositions and ionic conductivity of alluaudite-type double molybdates and tungstates

Cited by 35 publications

References 31 publications

Synthesis, crystal structures and properties of the new compounds K7–x Ag1+x (XO4)4 (X = Mo, W)

Synthesis, crystal structures and properties of the new compounds K7–x Ag1+x (XO4)4 (X = Mo, W)

Электронная структура и квадрупольные взаимодействия в перспективных катодных материалах Na-=SUB=-x-=/SUB=-M-=SUB=-y-=/SUB=-(MoO-=SUB=-4-=/SUB=-)-=SUB=-3-=/SUB=-, M=Mn, Fe, Co и Ni

Synthesis, Structure, and Conductivity of Alluaudite‐Related Phases in the Na2MoO4–Cs2MoO4–CoMoO4 System

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Synthesis, crystal structures and properties of the new compounds K_7–xAg_1+x(XO₄)₄ (X = Mo, W)

Synthesis, crystal structures and properties of the new compounds K_7–xAg_1+x(XO₄)₄ (X = Mo, W)

Synthesis, Structure, and Conductivity of Alluaudite‐Related Phases in the Na₂MoO₄–Cs₂MoO₄–CoMoO₄ System