Comparative Studies on Structure and Electronic Properties Between Thermal Lithiated Li_(0.5)MnO_2 and LiMn_2O_4

Monoclinic Li0.5MnO2 was synthesized by solid state reaction and the spectral and magnetic properties were studied in comparison with those of spinel LiMn2O4.The XRD pattern and Raman spectrum of Li0.5MnO2 are different from those of LiMn2O4,which indicate the different long-range and short-range crystal structure.XPS result shows the binding energies of 2p3/2 and 2p1/2 in Li0.5MnO2 are located at 642.3 and 653.6 eV,respectively.Through fitting the XPS spectra,the valence state of Mn ion in Li0.5MnO2 coincides with that in LiMn2O4.The high-temperature susceptibility of Li0.5MnO2 can be fitted by Curie-Weiss law whose Curie and Weiss constants are 33 A·m2·K/(mol·T) and-277(6) K,respectively.Although Li0.5MnO2 shows spin glass ground state,the transition temperature of Li0.5MnO2 is about 9 K lower than that of LiMn2O4.     

Valence determination of manganese in battery cathode materials by high-resolution Mn Kalpha1 spectra.

High-resolution the Mn Kalpha1 X-ray fluorescence spectra (HRXRF) were measured for a variety of manganese compounds, the oxidation number (valence) of which was from II to VII. Plots of the valence against the full width at half maximum (FWHM) and the chemical shift of the Kalpha1 X-ray fluorescence spectra give a curve and a liniar relation, respectively. The coefficient of correlation (R2) for the latter plot was 0.989 between valency II and VII. More excellent linearlity from III to IV was obtained with R2 = 0.995, which enabled us to determine the oxidation number of manganese atom in a nickel ion doped spinel structure, LiMn2O4 (LiNixMn(2-x)O4, with 0.2 < x < 0.42). From the valence of manganese ion obtained from HRXRF, the oxidation number of nickel ion is concluded to be divalent.     

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.     

Oxygen K-edge XANES investigation of NicMg(1-c)O solid solutions

A series of Ni(c)Mg(1-c)O solid solutions are characterized by means of synchrotron radiation X-ray diffraction and X-ray absorption near-edge-structure spectroscopy at oxygen K-edge (532 eV). A dramatic drop of the pre-edge peak intensity is observed in the Ni(c)Mg(1-c)O system upon dilution. It can be attributed to a decrease of 3d(8)(Ni(2+))-2p(O(2-)) mixing upon dilution with magnesium ions due to a decrease of the number of 3d vacancies as nickel ion is replaced by magnesium ion. Similarly, the decrease of the number of 4s and 4p vacancies also leads to a decrease of 4s4p(Ni(2+))-2p(O(2-)) hybridization, and hence a drop of intensities of features B and C. The features E and F are more sensitive to the increase of the degree of disorder upon dilution than feature D, revealing that the latter is mainly dependent by the medium-range order.     

Electronic structure of A- and B-site doped lanthanum manganites: a combined X-ray spectroscopic study

The electronic properties of a series of colossal magnetoresistance (CMR) compounds, namely LaMnO3, La(1-x)Ba(x)(MnO3 (0.2 < or = x < or = 0.55), La(0.76)Ba(0.24)Mn(0.84)Co(0.16)O3, and La(0.76)Ba(0.24)Mn(0.78)Ni(0.22)O3, have been investigated in a detailed spectroscopic study. A combination of X-ray photoelectron spectroscopy (XPS), X-ray emission spectroscopy (XES), X-ray absorption spectroscopy (XAS), and resonant inelastic X-ray scattering (RIXS) was used to reveal a detailed picture of the electronic structure in the presence of Ba, Co, and Ni doping in different concentrations. The results are compared with available theory. The valence band of La(1-x)()Ba(x)MnO3 (0 < or = x < or = 0.55) is dominated by La 5p, Mn 3d, and O 2p states, and strong hybridization between Mn 3d and O 2p states is present over the whole range of Ba concentrations. Co-doping at the Mn site leads to an increased occupancy of the e(g) states near the Fermi energy and an increase in the XPS valence band intensity between 0.5 and 5 eV, whereas the Ni-doped sample shows a lower density of occupied states near the Fermi energy. The Ni d states are located in a band spanning the energy range of 1.5-5 eV. XAS spectra indicate that the hole doping leads to mixed Mn 3d-O 2p states. Furthermore, RIXS at the Mn L edge has been used to probe d-d transitions and charge-transfer excitations in La(1-x)Ba(x)MnO3.     

锂离子电池掺钴正极材料电子结构的DV-Xα研究

The electronic structures of electrode material LiMn2O4 and Li5Mn7CoO8 for the lithium ion battery are studied by employing an ab initio “atomic-basis + norm-conserving non-local pseudopotentias” method. The calculation results of the electronic structure of an ode material LiMn2O4 show that the valence band of LiMn2O4 are mainly made up of 3d atomic orbtics of Mn(8) and Mn(9), and 2 p atomic orbits of O(7), O(6) and O(4), while the conduction band contains essentially 3d orbits of Mn (8) and Mn (9), and 2p atomic orbits of O(7). At the same time, the computing results of electronic structure of electrode material Li5Mn7CoO8 indicate that the reversible capacity of the electrode can decrease and discharge voltage reduces in the cycling, and the net charge of partial lithium ions of the active electrode material and the interaction between lithium ions and oxygen ions increase. While the cycling performance of the anode can improve due to the structural stabilization of the material Li5Mn7CoO8 corresponding to the decrease of the valence band width and enhancement of the Co-O bond.     

A time-resolved quadrupole mass spectrometric study on 355 nm laser ablated species ejected from LiMn2O4

Mass, velocity and angle distributions of the ablated species generated from 355 nm pulsed laser ablation of a LiMn2O4 target were investigated with an angle- and time-resolved mass spectrometric technique. Both neutral and ionic species of Li, O, LiO, LiO2, Mn, Li2, Li4, Li6, LiMn, MnO and MnO2 were observed at the laser fluence of 0.8 J · cm-2. The yield and variety of the ablated species increase with increasing the laser fluence. The time-of-flight spectra of ablated species can be fitted by a Maxwell-Boltzmann distribution with a center-of-mass velocity. There exist laser fluence thresholds for the ablated LiMn, Li2O and LiO2 species, and the fluence threshold of ionic species is higher than that of neutral species. The angular distributions of the ionic and neutral ablated species can be simulated by a cosnθor a bicosine function αcosθ+(1- α)cos"θ. In addition, the ablation mechanism of LiMn2O4 by a 355 nm pulsed laser is discussed.     

Electronic structure of ReO3Me by variable photon energy photoelectron spectroscopy,absorption spectroscopy and density functional calculations

Valence photoelectron (PE) spectra have been measured for ReO(3)Me using a synchrotron source for photon energies ranging between 20 and 110 eV. Derived branching ratios (BR) and relative partial photoionization cross sections (RPPICS) are interpreted in the context of a bonding model calculated using density functional theory (DFT). Agreement between calculated and observed ionization energies (IE) is excellent. The 5d character of the orbitals correlates with the 5p --> 5d resonances of the associated RPPICS; these resonances commence around 47 eV. Bands with 5d character also show a RPPICS maximum at 35 eV. The RPPICS associated with the totally symmetric 4a(1) orbital, which has s-like character, shows an additional shape resonance with an onset of 43 eV. The PE spectrum of the inner valence and core region measured with photon energies of 108 and 210 eV shows ionization associated with C 2s, O 2s, and Re 4f and 5p electrons. Absorption spectra measured in the region of the O1s edge showed structure assignable to excitation to the low lying empty "d" orbitals of this d(0) molecule. The separation of the absorption bands corresponded with the calculated orbital splitting and their intensity with the calculated O 2p character. Broad bands associated with Re 4d absorption were assigned to (2)D(5/2) and (2)D(3/2) hole states. Structure was observed associated with the C1s edge but instrumental factors prevented firm assignment. At the Re 5p edge, structure was observed on the (2)P(3/2) absorption band resulting from excitation to the empty "d" levels. The intensity ratios differed from that of the O 1s edge structure but were in good agreement with the calculated 5d character of these orbitals. An absorption was observed at 45 eV, which, in the light of the resonance in the 4a(1) RPPICS, is assigned to a 4a(1) --> ne, na(2) transition. The electronic structure established for ReO(3)Me differs substantially from that of TiCl(3)Me and accounts for the difference in chemical behavior found for the two complexes.     

Cu-Sn-P-LiMn2O4纳米复合材料镀层的XPS和AES研究

采用化学复合镀技术，在Q₂₃₅碳钢片表面制备了Cu-Sn-P-LiMn₂O₄纳米复合材料镀层。用扫描电子显微镜(SEM)观察外貌；称重法测定厚度；通过5% NaCl溶液、1% H₂S气体加速腐蚀试验、抗粘性试验及室温氧化试验等多种手段测定其性能。用X-射线光电子能谱(XPS)及俄歇电子能谱(AES)测定其价态及组成。结果表明:Cu-Sn-P-LiMn₂O₄纳米复合材料镀层的性     

氧化银纳米粒子的制备及其动态受激荧光

采用真空蒸发沉积法和辉光放电氧化法,制备了粒径在5～30 nm之间的可控、空间分布均匀、高纯度的氧化银纳米薄膜,使薄膜成岛状生长和避免光照是制备过程中的两个关键问题.用XPS分析了Ag 3d和O 1s轨道的结合能,计算了银和氧的原子比,证明其成分为Ag2O,用XRD确定了氧化银纳米薄膜最强的衍射峰分别对应Ag2O的（111）、（110）、（200）、（211）晶面族.研究了这种薄膜在可见光波段的光吸收,计算得氧化银的禁带宽度为2.8 eV.在蓝光持续照射几分钟激活后,观察到了其中纳米粒子在蓝光激发下发黄光和绿光,在绿光激发下发红光的现象,这种光致发光具有动态“闪烁”的特点.提出了氧化银光分解引入缺陷能级（如Ag3O, Ag2＋O和Ag3＋O）新的理论模型并对此现象进行定性的解释.     

甲烷氧化偶联催化剂Li/MgO的结构及表面性质的研究

本文用XRD、TEM、XPS和荧光光谱等方法研究了一组不同Li~+含量的Li/MgO催化剂的结构及表面性质,并与它们的氧化偶联甲烷的催化性能相关联。结果表明,低配位O~(2-)(O_(3c)~(2-))是使甲烷活化的活性中心。O_(1s)结合能为531.9eV的氧物种是对甲烷氧化偶联反应的C_2选择性起作用的活性氧物种。     

A Raman Study of Spinel LiMn2O4

A Raman study was carried out for LiMnzO4, which was synthesized via the mixture of Mn3O4 and LiNO3 sintered at different temperatures. It is shown that there are two kinds of Raman spectra for LiMn2O4 at different sintering temperatures, while the X-ray diffraction patterns of LiMnzO4 sintered at different temperatures are the same. Five Raman bands observed for the materials sintered below 500 ℃ are consistent with the theoretical prediction for spinel structure based on the group theory. Only two Raman bands were observed for the materials sintered at temperatures higher than 500 ℃. The best preparation condition for obtaining a good spinel LiMn2O4 is suggested based on the Raman study.     

Synthesis and characterization of phosphate-modified LiMn2O4 cathode materials for Li-ion battery

<正>LiMn_2O_4 spinel cathode materials were modified with 2 wt.%Li-M-PO_4(M=Co,Ni,Mn) by polyol synthesis method.The phosphate surface-modified LiMn_2O_4 cathode materials were physically characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM) and energy dispersive X-ray spectroscopy(EDS).The charge-discharge test showed that the cycling and rate capacities of LiMn_2O_4 cathode materials were significantly enhanced by stabilizing the electrode surface with phosphate.     

锂离子电池正极材料LiMn2O4的合成与晶体结构（英）

Spinel LiMn₂O₄ powders were prepared using two-step synthesis method consisting of solid-state reaction method and citrate modified sol-gel method. The effects of the calcination temperature and the Li/Mn ratio of raw materials were studied on the physicochemical and electrochemical properties of the spinel LiMn₂O₄ powders, such as crystallinity, lattice constant and density. The title compound was characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Polycrystalline LiMn₂O₄ powers calcined at 750 ℃ were found to be composed of very uniformly-sized microcrystal with an average particle size of 300 nm. The improvement in electrochemical properties was mainly attributed to the process of re-grinding by absolute alcohol.     

Spinel-to-CaFe2O4-type structural transformation in LiMn2O4 under high pressure

A new form of LiMn2O4 is reported. The structure is the CaFe2O4-type and 6% denser than the spinel. The structure transformation was achieved by heating at 6 GPa. Analysis of the neutron diffraction pattern confirmed an average of the structure; the unit cell was orthorhombic at a = 8.8336(5) angstroms, b = 2.83387(18) angstroms, and c = 10.6535(7) angstroms (Pnma). Electron diffraction patterns indicated an order of superstructure 3a x b x c, which might be initiated by Li vacancies. The exact composition is estimated at Li(0.92)Mn2O4 from the structure analysis and quantity of intercalated Li. The polycrystalline CaFe2O4-type compound showed semiconducting-like characters over the studied range above 5 K. The activation energy was reduced to approximately 0.27 eV from approximately 0.40 eV at the spinel form, suggesting a possible enhancement of hopping mobility. Magnetic and specific-heat data indicated a magnetically glassy transition at approximately 10 K. As the CaFe2O4-type transition was observed for the mineral MgAl2O4, hence the new form of the lithium manganese oxide would provide valuable opportunities to study not only the magnetism of strongly correlated electrons but also the thermodynamics of the phase transition in the mantle.     

脉冲激光沉积LiMn2O4薄膜的研究

在氧气氛下采用355nm脉冲激光烧蚀制备了LiMn₂O₄薄膜,并用四极质谱和发光光谱技术考察了脉冲激光烧蚀过程及环境氧气对薄膜沉积过程的影响.质谱测定结果表明,355nm激光烧蚀LiMn₂O₄的产物主要有Li⁺、Mn⁺等离子和O₂、O、LiO₂、LiMnO、MnO及锂原子的多聚体等中性产物.不同氧气压下测定的发光光谱表明烧蚀原子在环境氧气氛中存在氧化过程.用循环伏安法和X射线衍射法对薄膜进行了表征.     

Development of sample preparation technique to characterize chemical structure of humin by synchrotron-radiation–based X-ray photoelectron spectroscopy

Carbon-binding state of humin (HM, a non-conductive insoluble organo-mineral humic substance) was successfully characterized for the first time by synchrotron-radiation–based X-ray photoelectron spectroscopy (XPS). Four sample preparation techniques—HM on double-sided carbon tape, indium sheet, copper mesh, and in pellet formed from the mixture of HM and copper powder (Cu) at different mixing ratios (1:1, 1:2, and 1:6 v/v)—were compared. The results show that HM samples prepared using the first three methods had significant charge buildup, which made the interpretation of the XPS spectra impossible because of the shifts in the binding energy of C 1s XPS spectra. Pellets of HM:Cu mixture enhanced the electrical conductivity and reduced charge buildup on the sample surface. Pellets prepared with HM:Cu ratio of 1:1 (v/v) provided the minimum charge buildup and high sensitivity with difference in C 1s spectra regardless of the observing position. The C 1s spectra, estimated by the subtraction of the carbon contamination in Cu, showed the resolution of CC (284.0 eV), C C/C H (285.1 eV), C O (286.3 eV), CO (287.3 eV), and OC O (288.3 eV) and three additional peaks of CF (289.3 eV), CF₂ (290.2 eV), and CF₃ (291.4 eV). Soft X-ray absorption spectroscopic (XAS) analysis further proved the existence of fluoride (F 1s) in HM structure. The detection of fluorinated carbon in HM showed a great advancement of XPS compared with other conventional analyses. X-ray with the incident angle of 0° provided the smallest (nearly negligible) energy shift in the C 1s spectra of HM and did not damage the surface of the sample.     

锂嵌脱化合物LiMn2O4的微波烧结研究

本文用微波烧结法合成锂嵌脱材料ＬｉＭｎ２Ｏ４，研究了微波烧结功率，时间的固态产物相的影响，对ＬｉＭｎ２Ｏ４单相多晶粉末进行了ＸＲＤ，ＩＲＭ，ＸＰＳ，等离子体发射光谱及氧化还原等测试。     

Structural,optical and photoelectron spectroscopic studies of nano/micro ZnO:Cd rods synthesized via sol-gel route

Thin films of cadmium doped zinc oxide rod like microstructure have been synthesized by a very simple sol-gel dip coating technique. Sols were prepared from hydrated zinc oxide precursor and 2-methoxyethanol solvent with monoethanolamine as a sol stabilizer. XRD pattern confirmed the hexagonal wurtzite structure of the deposited ZnO films. Surface morphologies of the films have been studied by a scanning electron microscope and an atomic force microscope, which confirmed that the films are composed of densely packed randomly oriented nano/submicron rods with diameter in the range 300–400 nm having various lengths. We proposed a possible growth mechanism for this rodlike structure. X-ray photoelectron spectroscopic study was used to determine the binding energies and the Zn 2p3/2, Cd 3d5 and O 1s peaks in the XPS spectra were located at 1021.08 eV, 404.6 eV and 529.8 eV respectively, which confirmed the Cd doping in ZnO. Cadmium content in the film was estimated both from energy dispersive X-ray analysis and XPS measurement. Band gap energy determined from optical transmittance spectra systematically varied from 3.28 eV to 3.15 eV for 0% to 5.6% of Cd doping. Urbach parameter determined from the band tail of the transmittance spectra showed that it increased with doping percentage and this parameter for a fixed cadmium doping level decreased with increase of temperature.     

Core level studies of calcite and dolomite

Conventional X‐ray photoelectron spectroscopy (XPS) and synchrotron‐based X‐ray photoelectron spectroscopy (HRXPS) have been used to study Iceland spar calcite (CaCO₃) and dolomite (CaMg(CO₃)₂). The obtained full widths at half maximum (FWHMs) are mostly narrower than in the previous results, which together with the symmetry of the fitted peaks indicate effective neutralisation of surface charging. Some previously unidentified features observed in the Ca 2p, C 1s and O 1s spectra of calcite have been suggested to be bulk plasmons. Also, surface core level shifts in Ca 2p (in calcite) and Mg 2p (in dolomite) spectra have been obtained and found to be consistent between XPS and HRXPS measurements. A peak attributed to carbide (CaC₂) has been suggested to indicate beam‐assisted interaction with hydrocarbons found on the surface. Copyright © 2014 John Wiley & Sons, Ltd.