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Title: Crystal structure, phase relations and electrochemical properties of monoclinic Li{sub 2}MnSiO{sub 4}

Abstract

Phase relations in the MnO-SiO{sub 2}-Li{sub 4}SiO{sub 4} subsystem have been investigated by X-ray diffraction after solid-state reactions in hydrogen at 950-1150 deg. C. Both cation-deficient and cation-excess solid solutions Li{sub 2+2} {sub x} Mn{sub 1-} {sub x} SiO{sub 4} (-0.2{<=}x{<=}0.2) based on Li{sub 2}MnSiO{sub 4} have been found. According to Rietveld analysis, Li{sub 2}MnSiO{sub 4} (monoclinic, P2{sub 1}/n, a=6.3368(1), b=10.9146(2), c=5.0730(1) A, {beta}=90.987(1){sup o}) is isostructural with {gamma} {sub II}-Li{sub 2}ZnSiO{sub 4} and low-temperature Li{sub 2}MgSiO{sub 4}. All components are in tetrahedral environment, (MnSiO{sub 4}){sup 2-} framework is built of four-, six- and eight-member rings of tetrahedra. Testing Li{sub 2}MnSiO{sub 4} in an electrochemical cell showed that only 4% Li could be extracted between 3.5 and 5 V against Li metal. These results are discussed in comparison with those for recently reported orthorhombic layered Li{sub 2}MnSiO{sub 4} and other tetrahedral Li{sub 2} MXO{sub 4} phases. - Graphical abstract: Arrangement of Mn (large white balls) and Si (small grey balls) atoms in Li{sub 2}MnSiO{sub 4} structure. Bold lines connect atoms linked via common oxygen (not shown)

Authors:
 [1];  [2];  [1];  [1];  [1]
  1. Chemistry Faculty, Rostov State University, 7 ul. Zorge, Rostov-na-Donu 344090 (Russian Federation)
  2. Chemistry Faculty, Rostov State University, 7 ul. Zorge, Rostov-na-Donu 344090 (Russian Federation), E-mail: apetrenko@rsu.ru
Publication Date:
OSTI Identifier:
21015745
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 3; Other Information: DOI: 10.1016/j.jssc.2007.01.001; PII: S0022-4596(07)00015-1; Copyright (c) 2007 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ELECTROCHEMICAL CELLS; ELECTROCHEMISTRY; LITHIUM SILICATES; MANGANESE OXIDES; MONOCLINIC LATTICES; ORTHORHOMBIC LATTICES; SILICON OXIDES; SOLID SOLUTIONS; TEMPERATURE RANGE 1000-4000 K; X-RAY DIFFRACTION

Citation Formats

Politaev, V.V., Petrenko, A.A., Nalbandyan, V.B., Medvedev, B.S., and Shvetsova, E.S. Crystal structure, phase relations and electrochemical properties of monoclinic Li{sub 2}MnSiO{sub 4}. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2007.01.001.
Politaev, V.V., Petrenko, A.A., Nalbandyan, V.B., Medvedev, B.S., & Shvetsova, E.S. Crystal structure, phase relations and electrochemical properties of monoclinic Li{sub 2}MnSiO{sub 4}. United States. doi:10.1016/j.jssc.2007.01.001.
Politaev, V.V., Petrenko, A.A., Nalbandyan, V.B., Medvedev, B.S., and Shvetsova, E.S. Thu . "Crystal structure, phase relations and electrochemical properties of monoclinic Li{sub 2}MnSiO{sub 4}". United States. doi:10.1016/j.jssc.2007.01.001.
@article{osti_21015745,
title = {Crystal structure, phase relations and electrochemical properties of monoclinic Li{sub 2}MnSiO{sub 4}},
author = {Politaev, V.V. and Petrenko, A.A. and Nalbandyan, V.B. and Medvedev, B.S. and Shvetsova, E.S.},
abstractNote = {Phase relations in the MnO-SiO{sub 2}-Li{sub 4}SiO{sub 4} subsystem have been investigated by X-ray diffraction after solid-state reactions in hydrogen at 950-1150 deg. C. Both cation-deficient and cation-excess solid solutions Li{sub 2+2} {sub x} Mn{sub 1-} {sub x} SiO{sub 4} (-0.2{<=}x{<=}0.2) based on Li{sub 2}MnSiO{sub 4} have been found. According to Rietveld analysis, Li{sub 2}MnSiO{sub 4} (monoclinic, P2{sub 1}/n, a=6.3368(1), b=10.9146(2), c=5.0730(1) A, {beta}=90.987(1){sup o}) is isostructural with {gamma} {sub II}-Li{sub 2}ZnSiO{sub 4} and low-temperature Li{sub 2}MgSiO{sub 4}. All components are in tetrahedral environment, (MnSiO{sub 4}){sup 2-} framework is built of four-, six- and eight-member rings of tetrahedra. Testing Li{sub 2}MnSiO{sub 4} in an electrochemical cell showed that only 4% Li could be extracted between 3.5 and 5 V against Li metal. These results are discussed in comparison with those for recently reported orthorhombic layered Li{sub 2}MnSiO{sub 4} and other tetrahedral Li{sub 2} MXO{sub 4} phases. - Graphical abstract: Arrangement of Mn (large white balls) and Si (small grey balls) atoms in Li{sub 2}MnSiO{sub 4} structure. Bold lines connect atoms linked via common oxygen (not shown)},
doi = {10.1016/j.jssc.2007.01.001},
journal = {Journal of Solid State Chemistry},
number = 3,
volume = 180,
place = {United States},
year = {Thu Mar 15 00:00:00 EDT 2007},
month = {Thu Mar 15 00:00:00 EDT 2007}
}
  • Four new Li uranyl phosphates and arsenates have been prepared by high-temperature solid-state reactions: {alpha}-Li[(UO{sub 2})(PO{sub 4})] (1), {alpha}-Li[(UO{sub 2})(AsO{sub 4})] (2), {beta}-Li[(UO{sub 2})(AsO{sub 4})] (3) and Li{sub 2}[(UO{sub 2}){sub 3}(P{sub 2}O{sub 7}){sub 2}] (4). The structures of the compounds have been solved by direct methods: 1-triclinic, P1-bar, a=5.0271(1) A, b=9.8799(2) A, c=10.8920(2) A, {alpha}=108.282(9){sup o}, {beta}=102.993(8){sup o}, {gamma}=104.13(1){sup o}, V=470.69(2) A{sup 3}, Z=4, R{sub 1}=0.0415 for 2786 unique reflections with |F{sub 0}|{>=}4{sigma}{sub F}; 2-triclinic, P1-bar, a=5.129(2) A, b=10.105(3) A, c=11.080(3) A, {alpha}=107.70(2){sup o}, {beta}=102.53(3){sup o}, {gamma}=104.74(3){sup o}, V=501.4(3) A{sup 3}, Z=4, R{sub 1}=0.055 for 1431 unique reflections with |F{submore » 0}|{>=}4{sigma}{sub F}; 3-triclinic, P1-bar, a=5.051(1) A, b=5.303(1) A, c=10.101(1) A, {alpha}=90.31(1){sup o}, {beta}=97.49(1){sup o}, {gamma}=105.08(1){sup o}, V=258.80(8) A{sup 3}, Z=2, R{sub 1}=0.0339 for 2055 unique reflections with |F{sub 0}|{>=}4{sigma}{sub F}; 4-triclinic, P1-bar, a=5.312(1) A, b=6.696(1) A, c=12.542(1) A, {alpha}=94.532(9){sup o}, {beta}=99.059(8){sup o}, {gamma}=110.189(7){sup o}, V=409.17(10) A{sup 3}, Z=2, R{sub 1}=0.0565 for 1355 unique reflections with |F{sub 0}|{>=}4{sigma}{sub F}. The structures of all four compounds are based upon 3-D frameworks of U and T polyhedra (T=P, As). Phases 1 and 2 are isostructural and consist of U{sub 2}O{sub 12} dimers and UO{sub 6} square bipyramids linked by single TO{sub 4} tetrahedra. The structure of 3 consists of 3-D framework of corner-sharing UO{sub 6} bipyramids and AsO{sub 4} tetrahedra. In the structure of 4, the framework is composed of U{sub 2}O{sub 12} dimers, UO{sub 6} bipyramids and P{sub 2}O{sub 7} dimers. In all the compounds, Li{sup +} cations reside in framework cavities. The topologies of the 3-D frameworks can be described as derivatives of the PtS (cooperite) network. - Graphical abstract: Polyhedral and topological presentation of Li{sub 2}[(UO{sub 2}){sub 3}(P{sub 2}O{sub 7}){sub 2}] crystal structure.« less
  • Single crystals of LiCr(MoO{sub 4}){sub 2}, Li{sub 3}Cr(MoO{sub 4}){sub 3} and Li{sub 1.8}Cr{sub 1.2}(MoO{sub 4}){sub 3} were grown by a flux method during the phase study of the Li{sub 2}MoO{sub 4}-Cr{sub 2}(MoO{sub 4}){sub 3} system at 1023 K. LiCr(MoO{sub 4}){sub 2} and Li{sub 3}Cr(MoO{sub 4}){sub 3} single phases were synthesized by solid-state reactions. Li{sub 3}Cr(MoO{sub 4}){sub 3} adopts the same structure type as Li{sub 3}In(MoO{sub 4}){sub 3} despite the difference in ionic radii of Cr{sup 3+} and In{sup 3+} for octahedral coordination. Li{sub 3}Cr(MoO{sub 4}){sub 3} is paramagnetic down to 7 K and shows a weak ferromagnetic component below thismore » temperature. LiCr(MoO{sub 4}){sub 2} is isostructural with LiAl(MoO{sub 4}){sub 2} and orders antiferromagnetically below 20 K. The magnetic structure of LiCr(MoO{sub 4}){sub 2} was determined from low-temperature neutron diffraction and is based on the propagation vektor k{sup -}>=(1/2 ,1/2 ,0). The ordered magnetic moments were refined to 2.3(1) mu{sub B} per Cr-ion with an easy axis close to the [1 1 1-bar] direction. A magnetic moment of 4.37(3) mu{sub B} per Cr-ion was calculated from the Curie constant for the paramagnetic region. The crystal structures of the hitherto unknown Li{sub 1.8}Cr{sub 1.2}(MoO{sub 4}){sub 3} and LiCr(MoO{sub 4}){sub 2} are compared and reveal a high degree of similarity: In both structures MoO{sub 4}-tetrahedra are isolated from each other and connected with CrO{sub 6} and LiO{sub 5} via corners. In both modifications there are Cr{sub 2}O{sub 10} fragments of edge-sharing CrO{sub 6}-octahedra. - Graphical abstract: Magnetic structure of LiCr(MoO{sub 4}){sub 2}. The orientation of the magnetic moments of Cr{sup 3+} are shown by arrows.« less
  • X-ray investigation of solid state interaction of the components in the Li{sub 2}MoO{sub 4}–Rb{sub 2}MoO{sub 4}–Fe{sub 2}(MoO{sub 4}){sub 3} system was carried out, and a subsolidus phase diagram of the said system was constructed. The subsystem Rb{sub 2}MoO{sub 4}–LiRbMoO{sub 4}–RbFe(MoO{sub 4}){sub 2} was shown to be non-quasiternary. Formation of a novel triple molybdate LiRb{sub 2}Fe(MoO{sub 4}){sub 3} was established, conditions of solid state synthesis and crystallization of the compound were found. Its crystal structure (orthorhombic, space group Pnma, Z=4, a=24.3956(6), b=5.8306(1), c=8.4368(2) Å) represents a new structure type and includes infinite two-row ribbons ([Fe(MoO{sub 4}){sub 3}]{sup 3−}){sub ∞} parallel tomore » the b axis and composed of FeO{sub 6} octahedra, terminal Mo(3)O{sub 4} tetrahedra, and bridge Mo(1)O{sub 4} and Mo(2)O{sub 4} tetrahedra connecting two or three FeO{sub 6} octahedra. The ribbons are connected to form 3D framework via corner-sharing LiO{sub 4} tetrahedra. Rubidium cations are 11- and 13-coordinated and located in cavities of this heterogeneous polyhedral framework. - Graphical abstract: Exploring the Li{sub 2}MoO{sub 4}–Rb{sub 2}MoO{sub 4}–Fe{sub 2}(MoO{sub 4}){sub 3} system showed its partial non-quasiternarity and revealed a new compound LiRb{sub 2}Fe(MoO{sub 4}){sub 3} which was structurally studied. - Highlights: • The Li{sub 2}MoO{sub 4}–Rb{sub 2}MoO{sub 4}–Fe{sub 2}(MoO{sub 4}){sub 3} system study revealed a new compound LiRb{sub 2}Fe(MoO{sub 4}){sub 3}. • Its structure of a new type includes ribbons of FeO{sub 6} octahedra and MoO{sub 4} tetrahedra. • The ribbons are connected into a 3D framework via corner-sharing LiO{sub 4} tetrahedra.« less
  • Single crystals of the new compounds Li{sub 6}[(UO{sub 2}){sub 12}(PO{sub 4}){sub 8}(P{sub 4}O{sub 13})] (1), Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] (2), Li[(UO{sub 2}){sub 4}(AsO{sub 4}){sub 3}] (3) and Li{sub 3}[(UO{sub 2}){sub 7}(AsO{sub 4}){sub 5}O)] (4) have been prepared using high-temperature solid state reactions. The crystal structures have been solved by direct methods: 1-monoclinic, C2/m, a=26.963(3) A, b=7.063(1) A, c=19.639(1) A, beta=126.890(4){sup o}, V=2991.2(6) A{sup 3}, Z=2, R{sub 1}=0.0357 for 3248 unique reflections with |F{sub 0}|>=4sigma{sub F}; 2-triclinic, P1-bar, a=7.1410(8) A, b=13.959(1) A, c=31.925(1) A, alpha=82.850(2){sup o}, beta=88.691(2){sup o}, gamma=79.774(3){sup o}, V=3107.4(4) A{sup 3}, Z=2, R{sub 1}=0.0722 formore » 9161 unique reflections with |F{sub 0}|>=4sigma{sub F}; 3-tetragonal, I4{sub 1}/amd, a=7.160(3) A, c=33.775(9) A, V=1732(1) A{sup 3}, Z=4, R{sub 1}=0.0356 for 318 unique reflections with |F{sub 0}|>=4sigma{sub F}; 4-tetragonal, P4-bar, a=7.2160(5) A, c=14.6540(7) A, V=763.04(8) A{sup 3}, Z=1, R{sub 1}=0.0423 for 1600 unique reflections with |F{sub 0}|>=4sigma{sub F}. Structures of all the phases under consideration are based on complex 3D frameworks consisting of different types of uranium polyhedra (UO{sub 6} and UO{sub 7}) and different types of tetrahedral TO{sub 4} anions (T=P or As): PO{sub 4} and P{sub 4}O{sub 13} in 1, AsO{sub 4} and As{sub 2}O{sub 7} in 2, and single AsO{sub 4} tetrahedra in 3 and 4. In the structures of 1 and 2, UO{sub 7} pentagonal bipyramids share edges to form (UO{sub 5}){sub i}nfinity chains extended along the b axis in 1 and along the a axis in 2. The chains are linked via single TO{sub 4} tetrahedra into tubular units with external diameters of 11 A in 1 and 11.5 A in 2, and internal diameters of 4.1 A in 1 and 4.5 A in 2. The channels accommodate Li{sup +} cations. The tubular units are linked into 3D frameworks by intertubular complexes. Structures of 3 and 4 are based on 3D frameworks composed on layers united by (UO{sub 5}){sub i}nfinity infinite chains. Cation-cation interactions are observed in 2, 3, and 4. In 2, the structure contains a trimeric unit with composition [O=U(1)=O]-U(13)-[O=U(2)=O]. In the structures of 3 and 4, T-shaped dimers are observed. In all the structures, Li{sup +} cations are located in different types of cages and channels and compensate negative charges of anionic 3D frameworks. - Graphical abstract: The crystal structures of Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] separated into tubular units and intertubular complexes.« less
  • Orthorhombic lithium zinc molybdate was first chosen and explored as a candidate for double beta decay experiments with {sup 100}Mo. The phase equilibria in the system Li{sub 2}MoO{sub 4}-ZnMoO{sub 4} were reinvestigated, the intermediate compound Li{sub 2}Zn{sub 2}(MoO{sub 4}){sub 3} of the alpha-Cu{sub 3}Fe{sub 4}(VO{sub 4}){sub 6} (lyonsite) type was found to be nonstoichiometric: Li{sub 2-2x}Zn{sub 2+x}(MoO{sub 4}){sub 3} (0<=x<=0.28) at 600 deg. C. The eutectic point corresponds to 650 deg. C and 23 mol% ZnMoO{sub 4}, the peritectic point is at 885 deg. C and 67 mol% ZnMoO{sub 4}. Single crystals of the compound were prepared by spontaneous crystallizationmore » from the melts and fluxes. In the structures of four Li{sub 2-2x}Zn{sub 2+x}(MoO{sub 4}){sub 3} crystals (x=0; 0.03; 0.21; 0.23), the cationic sites in the face-shared octahedral columns were found to be partially filled and responsible for the compound nonstoichiometry. It was first showed that with increasing the x value and the number of vacancies in M3 site, the average M3-O distance grows and the lithium content in this site decreases almost linearly. Using the low-thermal-gradient Czochralski technique, optically homogeneous large crystals of lithium zinc molybdate were grown and their optical, luminescent and scintillating properties were explored. - Graphical abstract: The phase diagram of the system Li{sub 2}MoO{sub 4}-ZnMoO{sub 4} was revised, Li{sub 2-2x}Zn{sub 2+x}(MoO{sub 4}){sub 3} (0<=x<=0.28 at 600 deg. C) isotypical to alpha-Cu{sub 3}Fe{sub 4}(VO{sub 4}){sub 6} was found. Structural studies for x=0; 0.03; 0.21; 0.23 show consecutive increasing the number of vacancies and atomic displacement anisotropy in the face-shared octahedral columns. Large Li{sub 2}Zn{sub 2}(MoO{sub 4}){sub 3} crystals were grown and their optical, luminescent and scintillating properties were explored.« less