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Title: Magnetic structures of β{sub I}-Li{sub 2}CoSiO{sub 4} and γ{sub 0}-Li{sub 2}MnSiO{sub 4}: Crystal structure type vs. magnetic topology

Abstract

The magnetic structure and properties of the candidate lithium-ion battery cathode materials Pbn2{sub 1}(≡Pna2{sub 1}) Li{sub 2}CoSiO{sub 4} and P2{sub 1}/n Li{sub 2}MnSiO{sub 4} have been studied experimentally using low-temperature neutron powder diffraction and magnetometry. Both materials undergo long-range antiferromagnetic ordering, at 14 K and 12 K respectively, due to super–super-exchange mediated by bridging silicate groups. Despite having different crystal structures (wurtzite- vs. “dipolar”-type), Li{sub 2}CoSiO{sub 4} and Li{sub 2}MnSiO{sub 4} have the same topology in terms of magnetic interactions, and adopt collinear magnetic structures of the same type with the propagation vectors (0, 1/2, 1/2) and (1/2, 0, 1/2), respectively. The magnetic moments in the two materials are aligned in parallel and obliquely to the distorted closed-packed layers of oxygen atoms. The experimentally observed values of the ordered magnetic moments, 2.9 μ{sub B} and 4.6 μ{sub B}, are close to those expected for d{sup 7} Co{sup 2+} and d{sup 5} Mn{sup 2+}, respectively. - Graphical abstract: Despite the different crystal structures β{sub I}-Li{sub 2}CoSiO{sub 4} and γ{sub 0}-Li{sub 2}MnSiO{sub 4} have similar magnetic topology and as a result adopt magnetic structure of the same type. - Highlights: • Magnetic structures of Li{sub 2}CoSiO{sub 4} and Li{sub 2}MnSiO{sub 4} weremore » studied for the first time. • Both materials antiferromagnetically order around 12–14 K. • Despite different crystal structure magnetic structures are of the same type. • The fact is attributed to similar topology of magnetic interactions.« less

Authors:
 [1];  [2];  [3];  [2]
  1. Bragg Institute, Australian Nuclear Science and Technology Organisation, Lucas Heights, NSW 2234 (Australia)
  2. School of Chemistry, The University of Sydney, Sydney, NSW 2006 (Australia)
  3. (Malaysia)
Publication Date:
OSTI Identifier:
22443369
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 216; Other Information: Copyright (c) 2014 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; ANTIFERROMAGNETISM; ATOMIC FORCE MICROSCOPY; CATHODES; COBALT IONS; INTERACTIONS; LITHIUM; LITHIUM ION BATTERIES; MAGNETIC MOMENTS; MAGNETIC PROPERTIES; MANGANESE IONS; MONOCLINIC LATTICES; NEUTRON DIFFRACTION; ORTHORHOMBIC LATTICES; OXYGEN; SILICATES

Citation Formats

Avdeev, Maxim, E-mail: max@ansto.gov.au, Mohamed, Zakiah, Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, and Ling, Chris D.. Magnetic structures of β{sub I}-Li{sub 2}CoSiO{sub 4} and γ{sub 0}-Li{sub 2}MnSiO{sub 4}: Crystal structure type vs. magnetic topology. United States: N. p., 2014. Web. doi:10.1016/J.JSSC.2014.04.028.
Avdeev, Maxim, E-mail: max@ansto.gov.au, Mohamed, Zakiah, Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, & Ling, Chris D.. Magnetic structures of β{sub I}-Li{sub 2}CoSiO{sub 4} and γ{sub 0}-Li{sub 2}MnSiO{sub 4}: Crystal structure type vs. magnetic topology. United States. doi:10.1016/J.JSSC.2014.04.028.
Avdeev, Maxim, E-mail: max@ansto.gov.au, Mohamed, Zakiah, Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, and Ling, Chris D.. Fri . "Magnetic structures of β{sub I}-Li{sub 2}CoSiO{sub 4} and γ{sub 0}-Li{sub 2}MnSiO{sub 4}: Crystal structure type vs. magnetic topology". United States. doi:10.1016/J.JSSC.2014.04.028.
@article{osti_22443369,
title = {Magnetic structures of β{sub I}-Li{sub 2}CoSiO{sub 4} and γ{sub 0}-Li{sub 2}MnSiO{sub 4}: Crystal structure type vs. magnetic topology},
author = {Avdeev, Maxim, E-mail: max@ansto.gov.au and Mohamed, Zakiah and Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam and Ling, Chris D.},
abstractNote = {The magnetic structure and properties of the candidate lithium-ion battery cathode materials Pbn2{sub 1}(≡Pna2{sub 1}) Li{sub 2}CoSiO{sub 4} and P2{sub 1}/n Li{sub 2}MnSiO{sub 4} have been studied experimentally using low-temperature neutron powder diffraction and magnetometry. Both materials undergo long-range antiferromagnetic ordering, at 14 K and 12 K respectively, due to super–super-exchange mediated by bridging silicate groups. Despite having different crystal structures (wurtzite- vs. “dipolar”-type), Li{sub 2}CoSiO{sub 4} and Li{sub 2}MnSiO{sub 4} have the same topology in terms of magnetic interactions, and adopt collinear magnetic structures of the same type with the propagation vectors (0, 1/2, 1/2) and (1/2, 0, 1/2), respectively. The magnetic moments in the two materials are aligned in parallel and obliquely to the distorted closed-packed layers of oxygen atoms. The experimentally observed values of the ordered magnetic moments, 2.9 μ{sub B} and 4.6 μ{sub B}, are close to those expected for d{sup 7} Co{sup 2+} and d{sup 5} Mn{sup 2+}, respectively. - Graphical abstract: Despite the different crystal structures β{sub I}-Li{sub 2}CoSiO{sub 4} and γ{sub 0}-Li{sub 2}MnSiO{sub 4} have similar magnetic topology and as a result adopt magnetic structure of the same type. - Highlights: • Magnetic structures of Li{sub 2}CoSiO{sub 4} and Li{sub 2}MnSiO{sub 4} were studied for the first time. • Both materials antiferromagnetically order around 12–14 K. • Despite different crystal structure magnetic structures are of the same type. • The fact is attributed to similar topology of magnetic interactions.},
doi = {10.1016/J.JSSC.2014.04.028},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 216,
place = {United States},
year = {Fri Aug 15 00:00:00 EDT 2014},
month = {Fri Aug 15 00:00:00 EDT 2014}
}
  • 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 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
  • The recent discovery of high-temperature superconductors has stimulated the intense research in molecular complexes developed as precursors for high T[sub c] superconductors by chemical processes. While most of the complexes previously reported have been homonuclear species, the authors have been interested in multi-component molecular complexes containing barium, yttrium, and copper with structures resembling those of high-temperature superconductors. Such molecular complexes might not only find direct use as precursors but may also serve as molecular models for the study of chemical and physical properties of superconductors. Two pentanuclear copper-barium complexes of formulas BaCu[sub 4](bdmap)[sub 4](PyO)[sub 4](O[sub 2]CCF[sub 3])[sub 2] (1) andmore » BaCu[sub 4](deae)[sub 4](PyO)[sub 4](O[sub 2]CCF[sub 3])[sub 2] (2) have been synthesized by the reactions of Cu(OCH[sub 3])[sub 2] with Ba(O[sub 2]CCF[sub 3])[sub 2], 2-hydroxypyridine, and 1,3-bis(dimethylamino)-2-propanol (bdmapH) or 2-(diethylamino)ethanol (deaeH). Both compounds were characterized structurally. The barium ion is sandwiched between two dicopper anions, [Cu[sub 2]L[sub 2](PyO)[sub 2](O[sub 2]CCF[sub 3])][sup [minus]] (L = bdmap or deae) and coordinated by eight oxygen atoms. The oxygen atoms on the PyO[sup [minus]] ligands coordinate exclusively to the barium ion. 14 refs., 5 figs., 5 tabs.« 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
  • The chemistry of (..mu..-H)/sub 2/Rh/sub 2/(P(0-i-C/sub 3/H/sub 7/)/sub 3/)/sub 4/ with carbon monoxide is described. One equivalent of carbon monoxide irreversibly converted the dimer to (..mu..-H)/sub 2/Rh/sub 2/(..mu..-CO)(P(0-i-C/sub 3/H/sub 7/)/sub 3/)/sub 4/. The latter transformed slowly in solution to generate Rh/sub 2/(..mu..-CO)/sub 2/(P(0-i-C/sub 3/H/sub 7/)/sub 3/)/sub 4/ and a second species presumed to be a hydride. The 30-electron Rh/sub 2/(..mu..-CO)/sub 2/(P(0-i-C/sub 3/H/sub 7/)/sub 3/)/sub 4/ dimer reacted reversibly with carbon monoxide to give Rh/sub 2/(..mu..-CO)/sub 2/(CO)/sub 2/(P(0-i-C/sub 3/H/sub 7/)/sub 3/)/sub 4/; no fragmentation to mononuclear metal complexes in this reaction system was observed up to 70/sup 0/C. Excess carbon monoxidemore » did however elicit a fragmentation of the 30-electron complex, (..mu..-H)/sub 2/Rh/sub 2/(..mu..-CO)(P(0-i-C/sub 3/H/sub 7/)/sub 3/)/sub 4/. Reaction was rapid to give HRh(CO)(P(0-i-C/sub 3/H/sub 7/)/sub 3/)/sub 3/ and HRh(CO)/sub 2/(P(0-i-C/sub 3/H/sub 7/)/sub 3/)/sub 2/. The chemical and dynamic solution properties of these two mononuclear species is described; the properties of HRh(CO)(P(0-i-C/sub 3/H/sub 7/)/sub 3/)/sub 3/ diverge sharply for uranium and 16 other elements in sediments, and for uranium and 9 other elements in ground water. Mass spectrometry results are given for helium in ground water. Field measurements and observations are reported for each site. Analytical data and field measurements are presented in tables and maps. Uranium concentrations in the sediments which were above detection limits ranged from 0.10 t 51.2 ppM. The mean of the logarithms of the uranium concentrations was 0.53. A group of high uranium concentrations occurs near the junctions of quadrangles AB, AC, BB, a 200 mK. In case 2), x-ray studies of isotopic phase separation in /sup 3/He--/sup 4/He bcc solids were carried out by B. A. Fraass.« less