Li2MTiO4 (M=Mn, Fe, Co, Ni): New cation-disordered rocksalt oxides exhibiting oxidative deintercalation of lithium. Synthesis of an ordered Li2NiTiO4

We describe the synthesis and characterization of a new series of oxides, Li₂MTiO₄ (M=Mn, Fe, Co, Ni) that crystallize in the rocksalt structure. For M=Ni, we have also obtained a low-temperature modification that adopts a Li₂SnO₃-type structure. All the phases, excepting M=Ni, undergo oxidative deinsertion of lithium in air/O₂ at elevated temperatures (>150°C), yielding LiMTiO₄ (M=Mn, Fe) spinels and a spinel-like Li_1+xCoTiO₄ as final products.     

Phase diagrams in the quaternary systems M1−xCuxCr2X4 with M = Cd,Mn, and X = S,Se

The phase diagrams of the spinel systems Cd_1?xCu_xCr₂S₄, Cd_1?xCu_xCr₂Se₄, and Mn_1?xCu_xCr₂S₄ have been studied on the basis of X-ray powder photographs of quenched samples and high-temperature X-ray diffraction patterns. At room temperature the mutual solid solubilities of the metallic copper and the semiconducting cadmium and manganese spinels are only small (x < 0.05 and >0.95). The interchangeability, however, increases largely with increasing temperature. Complete series of mixed crystals, as in the Zn_1?xCu_xCr₂X₄ (X = S, Se) systems, however, are not formed. The solid solutions with x > 0.07 and <0.95, x > 0.095 and <0.90, and x > 0.36 and <0.87, respectively, formed at higher temperatures cannot be quenched to room temperature without decomposition. The unit cell dimensions of the spinel solid solutions studied obviously do not obey Vegard's rule.     

Cathodic materials for lithium-ion batteries based on spinels Li x Mn2−y Me y O4: Synthesis, phase composition, and structure of Li x Mn2−y Cr y O4 at x = 1.0−1.2 and y = 0−0.5

Extralithiated chromium-doped finely divided lithium-manganese spinels are synthesized as a result of a two-step solid-phase process with use made of the fusion-saturation method. The spinels are intended for application as cathodic materials in lithium-ion batteries. The phase composition and structural characteristics of samples of cathodic materials of the type Li _x Mn_2?y Cr _y O₄ are studied. The samples with x = 1.0?1.2 and y = 0?0.5 are characterized by phase purity and cubic syngony with parameter a = 0.817?0.823 nm and a disperseness equal to 1–2 nm. The maximum content of chromium and lithium in Li _x Mn_2?y Cr _y O₄ that does not lead to violation of cubic syngony is determined. Lithium excess in the cathodic material that does not exceed 0.2 formula units may be used for compensating the irreversible capacity. Replacing some manganese atoms by chromium may facilitate retention of the structures’s integrity in the course of cycling.     

Li+ ion conductivity in the system Li4SiO4Li3VO4

Two ranges of solid solutions were prepared in the system Li₄SiO₄Li₃VO₄: Li_4?xSi_1?xV_xO₄, 0 < x ? 0.37 with the Li₄SiO₄ structure and Li_3+yV_1?ySi_yO₄, 0.18 ? y ? 0.53 with a γ structure. The conductivity of both solid solutions is much higher than that of the end members and passes through a maximum at ～40Li₄SiO₄ · 60Li₃VO₄ with values of ～1 × 10^?5 ohm^?1 cm^?1 at 20°C, rising to ～4 × 10^?2 ohm^?1 cm^?1 at 300°C. These conductivities are several times higher than in the corresponding Li₄SiO₄Li₃(P,As)O₄ systems, especially at room temperature. The solid solutions are easy to prepare, are stable in air, and maintain their conductivity with time. The mechanism of conduction is discussed in terms of the random-walk equation for conductivity and the significance of the term c(1 ? c) in the preexponential factor is assessed. Data for the three systems Li₄SiO₄Li₃YO₄ (Y = P, As. V) are compared.     

Li and Li MAS NMR Studies on Fast Ionic Conducting Spinel-Type Li2MgCl4, Li2-xCuxMgCl4, Li2-xNaxMgCl4, and Li2ZnCl4

⁶Li and ⁷Li MAS NMR spectra including 1D-EXSY (exchange spectroscopy) and inversion recovery experiments of fast ionic conducting Li₂MgCl₄, Li_2-xCu_xMgCl₄, Li_2-xNa_xMgCl₄, and Li₂ZnCl₄ have been recorded and discussed with respect to the dynamics and local structure of the lithium ions. The chemical shifts, intensities, and half-widths of the Li MAS NMR signals of the inverse spinel-type solid solutions Li_2-xM^I_xMgCl₄ (M^I=Cu, Na) with the copper ions solely at tetrahedral sites and sodium ions at octahedral sites and the normal spinel-type zinc compound, respectively, confirm the assignment of the low-field signal to Li^tet of inverse spinel-type Li₂MgCl₄ and the high-field signal to Lioct as proposed by Nagel et al. (2000). In contrast to spinel-type Li_2-2xMg_1+xCl₄ solid solutions with clustering of the vacancies and Mg²⁺ ions, the Cu⁺ and Na⁺ ions are randomly distributed on the tetrahedral and octahedral sites, respectively. The activation energies due to the various dynamic processes of the lithium ions in inverse spinel-type chlorides obtained by the NMR experiments are E_a=6.6-6.9 and ΔG^*>79 KJ mol⁻¹ (in addition to 23, 29, and 75 kJmol-1 obtained by other techniques), respectively. The largest activation energy of >79 KJ mol⁻¹ corresponds to hopping exchange processes of Li ions between the tetrahedral 8a sites and the octahedral 16d sites. The smallest value of 6.6-6.9 KJ mol⁻¹, which was derived from the temperature dependence of both the spin-lattice relaxation times T₁ and the correlation times τ_C of Li^tet, reveals a dynamic process for the Li^tet ions inside the tetrahedral voids of the structure, probably between fourfold 32e split sites around the tetrahedral 8a site.     

Lithium-substituted cobalt oxide spinels LixM1−xCo2O4 (M = Co2+, Zn2+; 0 ≤ x ≤ 0.4)

Substitution of Li⁺ into Co₃O₄ and ZnCo₂O₄ gives rise to the solid solution series Li_xM_1?xCo₂O₄ (M = Co²⁺ or Zn²⁺) having the spinel structure upto x = 0.4. X-Ray diffraction intensities show that the spinel solid solutions are likely to have the following cation distributions: (Co²⁺)_t[Li⁺_xCo³⁺_2?3xCo⁴⁺_2x]₀O₄ and (Zn²⁺_1?xCo²⁺_x)_t[Li⁺_xCo³⁺_2?3xCo⁴⁺_2x]₀O₄. Electrical resistivity and Seebeck coefficient data indicate that the electron transport in these systems occurs by a small-polaron hopping mechanism.     

Synthesis and phase transition of Li-Mn-O spinels with high Li/Mn ratio by thermo-decomposition of LiMnC2O4(Ac)

LiMnC₂O₄(Ac) precursor in which Li⁺ and Mn²⁺ were amalgamated in one molecule was prepared by solid-state reaction at room-temperature using manganese acetate, lithium hydroxide and oxalic acid as raw materials. By thermo-decomposition of LiMnC₂O₄(Ac) at various temperatures, a series of Li_1+y[Mn_2−xLi_x]_16dO₄ spinels were prepared with Li₂MnO₃ as impurities. The structure and phase transition of these spinels were investigated by XRD, TG/DTA, average oxidation state of Mn and cyclic voltammeric techniques. Results revealed that the Li-Mn-O spinels with high Li/Mn ratio were unstable at high temperature, and the phase transition was associated with the transfer of Li⁺ from octahedral 16c sites to 16d sites. With the sintering temperature increasing from 450 to 850 °C, the phase structure varied from lithiated-spinel Li₂Mn₂O₄ to Li₄Mn₅O₁₂-like to LiMn₂O₄-like and finally to rock-salt LiMnO₂-like. A way of determining x with average oxidation state of Mn and the content of Li₂MnO₃ was also demonstrated.     

Surface degradation of fluoride conducting crystals MF2:UF4:CeF3 (M = Ca,Sr, Ba)

The ac electrical response of cell systems composed of single crystals of the concentrated solid solutions M_1?x?yU_xCe_yF_2+2x+y (M = Ca, Sr, Ba and 2.7 < 2x + y < 26.5 m/o), and ionically blocking electrodes has been studied as a function of frequency and temperature. At elevated temperatures the crystals react with traces of oxygen or water vapor. Complex admittance analysis reveals the formation of low-conducting surface layers, contrary to diluted solid solutions which under similar conditions react to form high-conducting surface layers (2). The activation enthalpy for the layer conductivity is substantially larger than that for the bulk conductivity, and equals that for interstitial fluoride ion motion in dilute solid solutions. A mechanism of charge compensation in the layers is presented. After reaction the solid solutions based on CaF₂ show also a surface electronic conductivity. Scanning electron micrographs clearly reveal the surface degradation.     

The structure of Li3.4Si0.7S0.3O4 by powder neutron diffraction

The structure of Li_4?2xSi_1?xS_xO₄ (x ≈ 0.32) has been determined from neutron powder diffraction studies at room temperature, 350, and 700°C. This compound, which is a member of the series of ionic-conducting solid solutions formed between Li₄SiO₄ and Li₂SO₄, is isostructural with Li₃PO₄. The space group is Pmnb, with a = 6.1701(1), b = 10.6550(2), c = 5.0175(1)Å at room temperature. The distribution of lithium ions suggests the occurrence of a defect cluster in which the inclusion of an interstitial lithium ion causes displacements of the adjacent lithium ions of the normal Li₃PO₄ structure. There appears to be little variation of the structure with temperature.     

Non-stoichiometric 1:2 ordered perovskites in the Ba(Li1/4Nb3/4)O3-Ba(Li2/5W3/5)O3 system

Although both end members in the (1−x)Ba(Li_1/4Nb_3/4)O₃-xBa(Li_2/5W_3/5)O₃ (BLNW) system adopt a hexagonal perovskite structure, B-site ordered cubic perovskites are formed for the majority of their solid solutions (0.238?x?0.833). Within this range, single-phase 1:2 order (, , ) is stabilized for 0.238?x?0.385. In contrast to all known A(B_1/3^IB_2/3^II)O₃ perovskites, the 1:2 ordered BLNW solid solutions do not include any composition with a 1:2 cation distribution and the structure exhibits extensive non-stoichiometry. Structure refinements support a model where Li and W occupy different positions and Nb is distributed on both sites, i.e. Ba[(Li_3/4+y/2Nb_1/4−y/2)_1/3(Nb_1−yW_y)_2/3]O₃ (y=0.21-0.35, where y=0.9x). The stabilization of the non-stoichiometric order arises from the large charge/size site differences; the loss of 1:2 order for W-rich compositions is related to local charge imbalances on the A-site sub-lattice. The range of single-phase 1:1 order is confined to x=0.833, (Ba(Li_3/4Nb_1/4)_1/2(W)_1/2)O₃), where the site charge/size difference is maximized and the on-site mismatches are minimized. The microwave dielectric loss properties of the ordered BLNW solid solutions are significantly inferior as compared to their stoichiometric counterparts.     

Construction of a double-layered tetrahedral network within a perovskite host: Two-step route to the alkali-metal-halide layered perovskite, (LixCl)LaNb2O7

A two-step topotactic route is used to construct lithium halide layers within a perovskite host. Initially RbLaNb₂O₇ is converted to (CuCl)LaNb₂O₇ by ion exchange and then reductive intercalation with n-butyllithium is used to form (Li_xCl)LaNb₂O₇. The copper metal byproduct from the reduction step is removed by treatment with iodine. Rietveld refinement of neutron powder diffraction data revealed that an alkali-halide double layer with LiO₂Cl₂ tetrahedra forms between the perovskite slabs. Compositional studies indicate that the range for x in (Li_xCl)LaNb₂O₇ is 2?x<4, which appears consistent with the neutron data where only one lithium site was found in the structure.     

Thermochemistry of Li1+xMn2−xO4 (0?x?1/3) spinel

Lithium substituted Li_1+xMn_2−xO₄ spinel samples in the entire solid solution range (0?x?1/3) were synthesized by solid-state reaction. The samples with x<0.25 are stoichiometric and those with x?0.25 are oxygen deficient. High-temperature oxide melt solution calorimetry in molten 3Na₂O·4MoO₃ at 974 K was performed to determine their enthalpies of formation from constituent binary oxides at 298 K. The cubic lattice parameter was determined from least-squares fitting of powder XRD data. The variations of the enthalpy of formation from oxides and the lattice parameter with x follow similar trends. The enthalpy of formation from oxides becomes more exothermic with x for stoichiometric compounds (x<0.25) and deviates endothermically from this trend for oxygen-deficient samples (x?0.25). This energetic trend is related to two competing substitution mechanisms of lithium for manganese (oxidation of Mn³⁺ to Mn⁴⁺ versus formation of oxygen vacancies). For stoichiometric spinels, the oxidation of Mn³⁺ to Mn⁴⁺ is dominant, whereas for oxygen-deficient compounds both mechanisms are operative. The endothermic deviation is ascribed to the large endothermic enthalpy of reduction.     

Determination of phase fields in the CsBr-Cs2ZnBr4-Cs2CdBr4-Cs2HgBr4 quaternary system

Phase equilibria in the CsBr-Cs₂ZnBr₄-Cs₂CdBr₄-Cs₂HgBr₄ quaternary system were studied by differential thermal analysis. The CsBr-Cs₂ZnBr₄-Cs₂HgBr₄ ternary system has a ternary eutectic, E ₁, at ～83 mol % Cs₂HgBr₄, 2 mol % Cs₂ZnBr₄, and 15 mol % CsBr with a melting point of ～415°C. The CsBr-Cs₂ZnBr₄-Cs₂CdBr₄ ternary system has a ternary eutectic, E ₂, at ～53.5 mol % Cs₂CdBr₄, 1.5 mol % Cs₂ZnBr₄, and 45 mol % CsBr with a melting point of ～450°C. The polythermal section Cs₃ZnBr₅-Cs₂CdBr₄-Cs₂HgBr₄ in the CsBr-Cs₂ZnBr₄-Cs₂CdBr₄-Cs₂HgBr₄ quaternary system was constructed and investigated. This section is a quasi-ternary system and is characterized by the formation of regions of solid solutions Cs₂Zn _x Cd _y Hg_{1?x ? y} Br₄ and solid solutions based on Cs₃ZnBr₅. The liquidus surface of the quaternary system consists of three fields of primary crystallization of cesium bromide, a solid solution Cs₂Zn _x Cd _y Hg_{1?x ? y} Br₄, and a solid solution based on Cs₃ZnBr₅.     

固体电解质Li9-nxMn+xN2Cl3(M=Na、Mg、Al)的合成及表征

高温固相反应合成了固体电解质Ｌｉ９－ｎｘＭ＾ｎ＋ｘＮ２Ｃｌ３（Ｍ＝Ｎａ、Ｍｇ、Ａｌ）。利用粉末Ｘ射线衍射测定样品结构,测定了离子电导率,分解电压和电子电导。得出掺杂可以提高快离子快离子导体材料Ｌｉ９Ｎ２Ｃｌ３中的Ｌｉ＾＋离子可以很大程度的提高其电导率。     

Composition and structure of acid leached LiMn2−yTiyO4 (0.2≤y≤1.5) spinels

Lithium manganese titanium spinels, LiMn_2−yTi_yO₄, (0.2≤y≤1.5) have been synthesized by solid-state reaction between TiO₂ (anatase), Li₂CO₃ and MnCO₃. Li⁺ was leached from the powdered reaction products by treatment in excess of 0.2 N HCl at 85 °C for 6 h, under reflux. The elemental composition of the acidic solution and solid residues of leaching has been determined by complexometric titration, atomic absorption spectroscopy and X-ray fluorescence analysis. Powder X-ray diffraction was used for structural characterization of the crystalline fraction of the solid residues. It has been found that the amount of Li⁺ leached from LiMn_2−yTi_yO₄ decreases monotonically with increasing y in the interval 0.2≤y≤1.0 and abruptly drops to negligibly small values for y>1.0. The content of Mn and Li in the liquid phase and of Mn and Ti in the solid (amorphous plus crystalline) residue, were related to the composition and cation distribution in the pristine compounds. A new formal chemical equation describing the process of leaching and a mechanism of the structural transformation undergone by the initial solids as a result of Li⁺ removal has been proposed.     

Festkörperreaktionen in Chalkogenidsystemen. V. Verteilungsgleichgewichte zweiwertiger Übergangsmetalle in Chromthiospinell-Mischkristallen

The solid-state equilibria of the chromium thiospinel solid solutions M_xM′_1?xCr₂S₄ (M,M′ = Mn, Co, Zn, Cd), with excess binary sulfides MS and M′S or M_1?xM′_xS mixed crystals, are investigated. At 600°C the following equilibrium compositions are found: Mn_0.38Co_0.62Cr₂S₄, Mn_0.36Zn_0.64Cr₂S₄, Mn_0.64Cd_0.36Cr₂S₄, Co_0.33Zn_0.67Cr₂S₄, Co_0.68Cd_0.32Cr₂S₄, and Zn_0.75Cd_0.25Cr₂S₄. The results show that metals with small crystal radii and high tetrahedral site preference energy are preferentially incorporated into the tetrahedral sites of chromium thiospinels. With increasing temperature the composition of the quaternary spinels approach M_0.5M′_0.5Cr₂S₄. From the temperature dependence of the equilibrium constants the reaction enthalpies could be determined. The binary sulfides MS and M′S are incompletely miscible excepting the system $\text{ZnS}\text{CdS}$. At 600°C the following miscibility gaps are found: Mn_yZn_1?yS: y = 0.43 – ≈ 1.0, Mn_yCd_1?yS: y = 0.50 – >0.9, Co_yMn_1?yS: y = <0.1 – ≈ 1.0, Co_yZn_t?yS: y = 0.1 – ≈ 1.0, and Co_yCd_1?yS: y = 0.1 – ≈ 1.0. With increasing temperature the miscibility gaps, especially of the systems with CoS, get smaller. The spinel solid solutions and the $\text{ZnS}\text{CdS}$ mixed crystals obey Vegard's rule.     

Revised phase diagram of Li2MoO4-ZnMoO4 system, crystal structure and crystal growth of lithium zinc molybdate

Orthorhombic lithium zinc molybdate was first chosen and explored as a candidate for double beta decay experiments with ¹⁰⁰Mo. The phase equilibria in the system Li₂MoO₄-ZnMoO₄ were reinvestigated, the intermediate compound Li₂Zn₂(MoO₄)₃ of the α-Cu₃Fe₄(VO₄)₆ (lyonsite) type was found to be nonstoichiometric: Li_2−2xZn_2+x(MoO₄)₃ (0≤x≤0.28) at 600 °C. The eutectic point corresponds to 650 °C and 23 mol% ZnMoO₄, the peritectic point is at 885 °C and 67 mol% ZnMoO₄. Single crystals of the compound were prepared by spontaneous crystallization from the melts and fluxes. In the structures of four Li_2−2xZn_2+x(MoO₄)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.     

Synthesis and crystal structure of Ln2MGe4O12, Ln=rare-earth element or Y; M=Ca, Mn, Zn

The crystal structure of the promising optical materials Ln₂M²⁺Ge₄O₁₂, where Ln=rare-earth element or Y; M=Ca, Mn, Zn and their solid solutions has been studied in detail. The tendency of rare-earth elements to occupy six- or eight-coordinated sites upon iso- and heterovalent substitution has been studied for the Y_2−xEr_xCaGe₄O₁₂ (x=0-2), Y_2−2xCe_xCa_1+xGe₄O₁₂ (x=0-1), Y₂Ca_1−xMn_xGe₄O₁₂ (x=0-1) and Y_2−xPr_xMnGe₄O₁₂ (x=0-0.5) solid solutions. A complex heterovalent state of Eu and Mn in Eu₂MnGe₄O₁₂ has been found.     

Phase relationships in the systems MSCr2S3In2S3 (M = Co,Cd, Hg)

The phase diagrams of the quaternary systems MSCr₂S₃In₂S₃, with M = Co, Cd, and Hg, were studied with the help of X-ray powder photographs of quenched samples, high-temperature X-ray diffraction patterns, DTA and TG measurements, and far-infrared spectra. Because indium sulfides do react with silica tubes, alumina crucibles must be used for annealing the samples. Complete series of mixed crystals are formed among the spinel-type compounds MCr₂S₄, MIn₂S₄ (M = Cd, Hg), and In₂S₃. HgIn₂S₄ is decomposed at temperatures above 300°C. In the sections CoCr₂S₄CoIn₂S₄ and CoCr₂S₄In₂S₃ relatively large miscibility gaps exist due to the change from normal to inverse spinel structure. But the interchangeability of both systems increases with increasing temperature, and at temperatures above 1000°C, complete series of solid solutions are formed, which can be quenched to ambient temperature. Superstructure ordering like that of ordered α-In₂S₃ has been found in the In-rich region of the MIn₂S₄In₂S₃ solid solutions. The unit cell dimensions of all stoichiometric and phase boundary compounds, e.g., Cd_1.15In_1.9S₄, including the chromium spinels MCr₂S₄ (M = Mn, Zn) and ZnCr₂Se₄, are given and discussed in terms of possible deviations from stoichiometry.     

Binary systems with Li2SO4 as one of the components

Six binary systems were studied using DTA with supplementary XRD. In Li₂SO₄?MSO₄ systems (M=Mg, Co, Ni), a primary solid solution with α-Li₂SO₄ structure (high-temperature form) and an incongruent melting compound Li₂M_y(SO₄)_1+y exist:y=2 with Mg andy=1 with Co and Ni. In Li₂SO₄?Li₃XO₄ systems (X=P, V), which are very different from one another, only primary solid solutions exist. In the Li₂SO₄?Li₂B₄O₇ system there is neither a solid solution nor an intermediate compound. Comparisons with previous investigations are made.