Influence of sequential lithium insertions on the physical properties of spinel manganese oxide

We present first principles studies based on density functional theory (DFT) to investigate the lithium intercalation process in spinel manganese oxide compound. The lattice volume change, energetics, and insertion voltage were systematically examined upon sequential lithium insertions into the lattice. The charge transfer mechanism upon lithium intercalation was studied by analyzing the calculated spectra of density of states. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Hydrothermal synthesis of nanostructured spinel lithium manganese oxide

Nanostructured spherical spinel lithium manganese oxide (LiMnO) with about 200 nm in diameter was synthesized for the first time by mild hydrothermal method. The formation of the nanostructured spheres was through self-assembly of the nanoparticles and nanobelts. The influence of the reaction temperature and the time of formation of the nanostructures have been systematically studied. The thermal stability of the nanostructures has been examined by heating-treatment at different temperatures. Powder X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, thermogravimetric analysis and inductively coupled plasma-atomic emission spectroscopy were used to characterize the products.     

Confined growth of lithium manganese oxide nanoparticles

Nanostructures of single crystallites of spinel LiMn₂O₄ (LMO) were prepared by the simple pyrolysis of aqueous solution of LiNO₃ and Mn(NO₃)₂ in a confined space such as either droplets or mesopores. When the mixed nitrate solution was spray pyrolyzed at temperatures below 700 °C, 1-μm LMO spheres were obtained consisting of ~20-nm single crystallites randomly packed. Such LMO phase, once obtained, would sustain for further heat-treatment. Next, new spraying solution was prepared by adding the precursor for mesoporous silica (MPS) to the nitrates solution. By spray pyrolyzing such solution, LMO was impregnated inside pores of the MPS being structured. The silica could be removed by subsequent NaOH treatment to leave spherical LMO mesophase. The nitrates was also able to soak into the existing MPS having cylindrical pores and form short isolated LMO chains in the mesopores by the subsequent heating. After the same NaOH treatment, the LMO phase turned into bundles of very ‘long’, and often straight, chains, consisting of 8-nm LMO nanoparticles. This will be elucidated through further study.     

Structural disorder along the lithium diffusion pathway in cubically stabilized lithium manganese spinel II. Molecular dynamics calculation

Molecular dynamics (MD) simulations were carried out to investigate the local structural disorder in LiMn₂O₄ spinel. Small but significant shifts of lithium and oxygen atom positions from the high symmetry sites of the lattice were observed. The lithium atoms are displaced approximately 0.16 Å away from 8a site of the lattice and are shifted along the diffusion pathway towards the face midpoints of the coordinating LiO₄ tetrahedra. A diffuse population of Li atoms was also detected centered about 0.38 Å away from the 16c octahedral vacancy, suggesting a portion of the Li atoms are free from their tetrahedral cages at room temperature. The tetrahedrally coordinated O atoms are displaced by as much as 0.12 Å when bonded to one Li and three Mn atoms in identical oxidation states. On the other hand, if the coordinating Mn atoms are in mixed oxidation states, much larger O atom shifts of 0.22 Å are observed. Structural features obtained in this MD simulation, especially the off-center displacements of Li and O atoms, are in accord with the electron density distribution study of cubically stabilized Mg-doped LiMn₂O₄ spinel reported in Part I.     

Dynamics of three-component exchange on a cationite with lithium manganese spinel structure

The dynamics of the sorption of lithium ions on a cationite with lithium manganese spinel structure from neutral solutions against the background of a large amount of sodium ions was studied. It was demonstrated that the dynamics of the ion exchange of these ions from their mixed solutions differs significantly from that observed for their individual solutions. The experimental results can be explained by assuming that, at a large concentration of sodium ions in the solution, they saturate the surface of the cationite and that lithium ions are predominantly exchanged for sodium ions. This assumption is supported by the results of a mathematical modeling.     

The effect of chromium substitution on the phase transition of lithium manganese spinel oxides

The phase transition of chromium substituted lithium manganese spinel oxide, LiCr_yMn_2−yO₄ was investigated by low-temperature powder X-ray diffractometry (XRD), differential scanning calorimetry (DSC), and electrical resistivity measurements. The sample prepared at 820 °C resulted in lowering the transition temperature T_t with Cr composition y, whereas T_t of the sample prepared at 750 °C remained constant for 0≤y≤0.17 in LiCr_yMn_2−yO₄. This would be caused by a difference in distribution of the substituted Cr³⁺ ion in octahedral site depending on the preparation temperature. The phase transition was suppressed with increasing the amount of Cr content.     

Rapid evaluation of charge/discharge properties for lithium manganese oxide particles at elevated temperatures

A microelectrode technique was applied to investigate the electrochemical properties of LiMn₂O₄ particles at elevated temperatures. Cyclic voltammograms of LiMn₂O₄ were measured after the particles were exposed to the electrolytes. This technique results in rapid and precise evaluation of the redox behavior of the materials. A significant capacity fading was observed in 1 M LiPF₆/EC+PC electrolytic solution, which indicates that both LiMn₂O₄ and LiPF₆ participate in the reaction to produce an inert material on the particle surface. Next, the capacity fading for two different BET surface area particles were compared using 1 M LiPF₆/EC+PC at 50 °C. The reaction was found not to be controlled by the surface area. Finally, a Li_1.1Mn_1.9O₄ particle was employed. The fading in discharge was ca. 10% for 50 cycles even at 50 °C, which means that the partial substitution of Mn in LiMn₂O₄ by Li substantially enhanced the capacity stability. Electronic Publication     

Lithium–manganese–nickel-oxide electrodes with integrated layered–spinel structures for lithium batteries

A series of lithium–manganese–nickel-oxide compositions that can be represented in three-component notation, xLi[Mn_1.5Ni_0.5]O₄ · (1 − x){Li₂MnO₃ · Li(Mn_0.5Ni_0.5)O₂}, in which a spinel component, Li[Mn_1.5Ni_0.5]O₄, and two layered components, Li₂MnO₃ and Li(Mn_0.5Ni_0.5)O₂, are structurally integrated in a highly complex manner, have been evaluated as electrodes in lithium cells for x = 1, 0.75, 0.50, 0.25 and 0. In this series of compounds, which is defined by the Li[Mn_1.5Ni_0.5]O₄–{Li₂MnO₃ · Li(Mn_0.5Ni_0.5)O₂} tie-line in the Li[Mn_1.5Ni_0.5]O₄–Li₂MnO₃–Li(Mn_0.5Ni_0.5)O₂ phase diagram, the Mn:Ni ratio in the spinel and the combined layered Li₂MnO₃ · Li(Mn_0.5Ni_0.5)O₂ components is always 3:1. Powder X-ray diffraction patterns of the end members and the electrochemical profiles of cells with these electrodes are consistent with those expected for the spinel Li[Mn_1.5Ni_0.5]O₄ (x = 1) and for ‘composite’ Li₂MnO₃ · Li(Mn_0.5Ni_0.5)O₂ layered electrode structures (x = 0). Electrodes with intermediate values of x exhibit both spinel and layered character and yield extremely high capacities, reaching more than 250 mA h/g with good cycling stability between 2.0 V and 4.95 V vs. Li° at a current rate of 0.1 mA/cm².     

Role of local and electronic structural changes with partially anion substitution lithium manganese spinel oxides on their electrochemical properties: X-ray absorption spectroscopy study

The electronic and local structures of partially anion-substituted lithium manganese spinel oxides as positive electrodes for lithium-ion batteries were investigated using X-ray absorption spectroscopy (XAS). LiMn(1.8)Li(0.1)Ni(0.1)O(4-η)F(η) (η = 0, 0.018, 0.036, 0.055, 0.073, 0.110, 0.180) were synthesized by the reaction between LiMn(1.8)Li(0.1)Ni(0.1)O(4) and NH(4)HF(2). The shift of the absorption edge energy in the XANES spectra represented the valence change of Mn ion with the substitution of the low valent cation as Li(+), Ni(2+), or F(-) anion. The local structural change at each compound with the amount of a Jahn-Teller Mn(3+) ion could be observed by EXAFS spectra. The discharge capacity of the tested electrode was in the order of LiMn(2)O(4) > LiMn(1.8)Li(0.1)Ni(0.1)O(4-η)F(η) (η = 0.036) > LiMn(1.8)Li(0.1)Ni(0.1)O(4) while the cycleability was in the order of LiMn(1.8)Li(0.1)Ni(0.1)O(4-η)F(η) (η = 0.036) ≈ LiMn(1.8)Li(0.1)Ni(0.1)O(4) > LiMn(2)O(4). It was clarified that LiMn(1.8)Li(0.1)Ni(0.1)O(4-η)F(η) has a good cycleability because of the anion doping effect and simultaneously shows acceptable rechargeable capacity because of the large amount of the Jahn-Teller Mn(3+) ions in the pristine material.     

Nanostructured amorphous manganese oxide cryogel as a high-rate lithium intercalation host

Amorphous manganese oxides have received increasing attention in recent years as high-capacity intercalation cathodes for rechargeable lithium batteries. Nanostructured electrodes have been shown to exhibit enhanced rate capabilities. In this paper, a nanostructured amorphous manganese oxide cryogel is reported that combines the advantages of the amorphous structure and the nano-architecture, leading to high lithium intercalation capacity and high rate capability. The cryogel is prepared by freeze-drying a Mn(IV) oxide hydrogel formed in situ via reduction of sodium permanganate solution with solid fumaric acid. The cryogel exhibits a nanoporous structure and a specific surface area of 350 m²/g. X-ray and electron diffraction reveals the amorphous nature of this freeze-dried gel. The material exhibits specific capacities of 289, 217 and 174 mAh/g at C/100, C/5 and 2C rates, respectively, demonstrating high capacity and excellent rate capability. This work shows the feasibility of the freeze-drying method for obtaining manganese oxides with nano-architecture and high specific surface area, and suggests the promise of the synthesis route to nanostructured amorphous manganese oxides via a hydrogel.     

Separation of lithium and magnesium isotopes by hydrous manganese(IV) oxide

Lithium and magnesium isotopes were separated by chemical ion exchange using hydrous manganese(IV) oxide and elution chromatography. The capacity of manganese(IV) oxide was 0.5 meq/g. The glass ion exchange column used was 35 cm long with an inner diameter of 0.2 cm, and 2.0M CH₃COONH₄ solution served as eluent. The single stage separation factor was determined from the elution curves and isotopic assays according to the method of Glueckauf. The separation factor of ⁶Li⁺-⁷Li⁺ was 1.022±0.002, those of ²⁴Mg²⁺-²⁵Mg²⁺, ²⁴Mg²⁺-²⁶Mg²⁺, and ²⁵Mg²⁺-²⁶Mg²⁺ were 1.012±0.001, 1.021±0.002, and 1.011±0.001, respectively.     

New large-scale production route for synthesis of lithium nickel manganese cobalt oxide

The spray roasting process is recently applied for production of catalysts and single metal oxides. In our study, it was adapted for large-scale manufacturing of a more complex mixed oxide system, in particular symmetric lithium nickel manganese cobalt oxide (LiNi_1/3Co_1/3Mn_1/3O₂—NMC), which is already used as cathode material in lithium-ion batteries. An additional lithiation step was coupled with the main process in order to obtain the desired layered structure. Thermogravimetric analysis and high-temperature X-ray diffractometry built the basis for determining suitable synthesis temperature regions for the used chloride precursors and the post-treatment step. The optimized process was proven on an industrial pilot line where a setup for minimum production capacity of 12 kg h^?1 was possible. The powder obtained directly after roasting had a very striking morphology compared to the final lithiated product. Hollow aggregates (≥250 μm) with overall 10.926 m² g^?1 surface area and a pore diameter of 3.396 nm were observed. Their well-faceted primary particles were converted into nanosized spheres after lithiation, building a few micrometer big high-porous agglomerates. Actual composition was verified by inductively coupled plasma atomic emission spectroscopy analysis, and the crystal structure and corresponding unit cell parameters were identified and confirmed by Rietveld fit of the derived X-ray diffraction pattern. The initial electrochemical measurements show a 149-mAh g^?1discharge capacity, as determined from cyclic voltammetry.     

Lithium manganese oxide with excellent electrochemical performance prepared from chemical manganese dioxide for lithium ion batteries

Chemical manganese dioxide (CMD) is synthesized by the SEDEMA process and adopted as a precursor for lithium manganese oxide with a spinel structure (LMO). LMO is also prepared from electrolytic manganese dioxide (EMD) as a reference for comparison. X-ray diffraction (XRD) shows that CMD is composed of γ-MnO₂, and scanning electron microscopy (SEM) with transmission electron microscopy (TEM) shows that the nanorods cover a spherical core with a diameter < 1 μm. The LMO prepared from CMD shows a much better rate capability and cycle life performance than that from EMD at high temperatures and high current densities. The excellent electrochemical performance is attributed to the structural stability during charge and discharge and the morphology of the LMO, a loose aggregation of the octahedral particles with a uniform size (<1 μm) and shape, which originated from that of CMD.     

Variations of electrical properties and chemical composition of the FeCr2S4 spinel

In its stability domain (medium or high sulfur pressures) between 600 °C and 1000 °C, FeCr₂S₄(spinel type) is a weak p-type non-stoichiometric semiconductor. Its conductivity is an average one (2.3<logσ(Ωm)⁻¹<3.3). Its chemical composition (x in the formula FeCr₂S_x) extends from 4.00 to 4.12. At constant chemical composition, the conductivity versus temperature follows the law σ = σ₀ exp(−ε/kT) with ε = 0.69 eV. Under low pressure the formation of interstitial chromium (point defects n) destroys the lattice leading to complete decomposition.     

Investigation of structural and magnetic properties of nanocrystalline manganese substituted lithium ferrites

Nanocrystalline manganese substituted lithium ferrites Li_0.5Fe_2.5−xMn_xO₄ (2.5≤x≥0) were prepared by sol-gel auto-combustion method. X-ray diffraction patterns revealed that as the concentration of manganese increased, the cubic phase changed to tetragonal. Magnetic properties were measured by hysteresis loop tracer technique. All the compositions indicated ferrimagnetic nature. The surface morphology of all the samples was studied by using scanning and transmission electron microscopy. The substitution of manganese ions in the lattice affected the structural as well as magnetic properties of spinels.     

氧化锰团簇粒子在有序多孔氧化锆孔道中的组装及其特殊性能研究

利用醇溶液浸渍法及后续的热处理工艺成功实现了氧化锰团簇粒子在有序多孔氧化锆孔道中的组装，借助XRD，TEM，UV-vis，EPR以及O~2-TPD等分析手段进行样品结构表征及性能分析。研究表明，氧化锰团簇粒子能比较均匀地分散于规则的孔道中；团簇粒子的生长随着热处理温度的提高受到孔道大小的限制；孔道中的氧化锰团簇粒子能显示出与较大尺寸氧化锰粒子完全不同的强顺磁信号，并且还具有优异的表面氧吸附特性。     

Effect of lithium oxide dopants on electrophysical and sorption properties of zinc oxide

The effects of lithium oxide dopants (0.5–0.8 at. % Li) on the electrophysical and sorption properties of ZnO were studied in the temperature range from 150 °C to 410 °C. The introduction of lithium increases the activation energy of the conductivity of ZnO, decreases its conductivity, and increases the amount of S0₂ sorbed. Two forms of chemisorbed SO₂ (donor and acceptor) are observed on the surface.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1096–1100, May, 1996.     

Electronic structure and magnetic properties of small manganese oxide clusters

To investigate the electronic structure and magnetic properties of manganese oxide clusters, we carried out first-principles electronic structure calculations for small MnO clusters. Among various structural and magnetic configurations of the clusters, the bulklike [111]-antiferromagnetic ordering is found to be favored energetically, while the surface atoms of the clusters exhibit interesting electronic and magnetic characteristics which are different from their bulk ones. The distinct features of the surface atoms are mainly attributed to the reduction of Mn coordination numbers and the bond-length contractions in the clusters, which may serve as a key factor for the understanding of physical and chemical properties of magnetic oxide nanoparticles.     

Nano-sized lithium manganese oxide dispersed on carbon nanotubes for energy storage applications

Nano-sized lithium manganese oxide (LMO) dispersed on carbon nanotubes (CNT) has been synthesized successfully via a microwave-assisted hydrothermal reaction at 200 °C for 30 min using MnO₂-coated CNT and an aqueous LiOH solution. The initial specific capacity is 99.4 mAh/g at a 1.6 C-rate, and is maintained at 99.1 mAh/g even at a 16 C-rate. The initial specific capacity is also maintained up to the 50th cycle to give 97% capacity retention. The LMO/CNT nanocomposite shows excellent power performance and good structural reversibility as an electrode material in energy storage systems, such as lithium-ion batteries and electrochemical capacitors. This synthetic strategy opens a new avenue for the effective and facile synthesis of lithium transition metal oxide/CNT nanocomposite.