Structural and magnetic properties of LiNi0.5Mn1.5O4 and LiNi0.5Mn1.5O4-δ spinels： A first-principles study

<正>Structural and magnetic properties of LiNi_0.5Mn_1.5O₄ and LiNi_0.5Mn_1.5O_4-δ are investigated using densityfunctional theory calculations.Results indicate that nonstoichiometric LiNi_0.5Mn_1.5O_4-δ and stoichiometric LiNi_0.5Mn_1.5O₄ exhibit two different structures,i.e.,the face-centred cubic（Fd-3m） and primitive,or simple,cubic （P4₃32） space groups,respectively.It is found that the magnetic ground state of LiNi_0.5Mn_1.5O₄（P4₃32 and Fd-3m） is a ferrimagnetic state in which the Ni and Mn sublattices are ferromagnetically ordered along the[110]direction whereas they are antiferromagnetic with respect to each other.We demonstrate that it is the presence of an O-vacancy in LiNi_0.5Mn_1.5O_4-δ with the Fd-3m space group that results in its superior electronic conductivity compared with LiNi_0.5Mn_1.5O₄ with the P4₃32 space group.     

Capacity fading reason of LiNi0.5Mn1.5O4 with commercial electrolyte

The cycling performances of LiNi_0.5Mn_1.5O₄ (LNMO) were investigated and the reasons of capacity fading were discussed. The results show that LNMO can deliver about 115 mAh?g^?1 at 1C at different temperatures; however, it retains only 61.57 % of its initial capacity after 130th cycles at 60 °C, which is much lower than 94.46 % of LNMO at 25 °C, and the cycling performance at 1C is better than that at 0.5C. The reason of capacity fading of LNMO at 60 °C is mainly due to the lower decomposition voltage of 4.3 V with commercial electrolyte and the larger decomposition current, of which the electrolyte decomposes and interacts with active materials to lead to the larger irreversible capacity loss. While the worse cycling performance at low rate is attributed to the longer interaction time between the electrolyte with the decomposition voltage of 4.5 V and the active materials.     

LiNi_(0.5)Mn_(0.5)O_2制备及表征

采用共沉淀法制备了LiNi0.5Mn0.5O2.XRD,Raman测试都表明材料是六方结构.XPS检测得出镍主要以正二价存在,锰元素主要以正四价存在.合成的LiNi0.5Mn0.5O2得到了50次的循环,但比容量较低.充放电循环性能比较研究表明,经过40次循环后,0.3,0.6,1.5 C的放电比容量分别是65.88,61.56,52.23 mA.h.g-1.     

Study on the electrochemical performance of LiNi0.5Mn1.5O4 with different precursor

LiNi_0.5Mn_1.5O₄ cathodes were synthesized by three different raw materials at high temperature. The samples were characterized by X-ray diffraction and scanning electron microscopy tests, respectively. The results indicate that the synthesized samples show pure spinel structure, and the samples synthesized by nickel?Cmanganese hydrate and nickel?Cmanganese oxide show regular geometrical shape. The electrochemical performance of sample synthesized by nickel?Cmanganese oxide is best. The first discharge capacity is 141 mAh/g, and the capacity retention is 98.6% after 50 cycles at 0.5?C rate. The discharge capacity at 5?C rate is still 120 mAh/g. Better crystallization, smaller specific surface area, and lower polarization may be responsible for the excellent electrochemical performance of the LiNi_0.5Mn_1.5O₄.     

Structure and insertion properties of disordered and ordered LiNi0.5Mn1.5O4 spinels prepared by wet chemistry

We present the synthesis, characterization, and electrode behavior of LiNi_0.5Mn_1.5O₄ spinels prepared by the wet-chemical method via citrate precursors. The phase evolution was studied as a function of nickel substitution and upon intercalation and deintercalation of Li ions. Characterization methods include X-ray diffraction, SEM, Raman, Fourier transform infrared, superconducting quantum interference device, and electron spin resonance. The crystal chemistry of LiNi_0.5Mn_1.5O₄ appears to be strongly dependent on the growth conditions. Both normal-like cubic spinel [Fd3m space group (SG)] and ordered spinel (P4 ₁ 32 SG) structures have been formed using different synthesis routes. Raman scattering and infrared features indicate that the vibrational mode frequencies and relative intensities of the bands are sensitive to the covalency of the (Ni, Mn)-O bonds. Scanning electron microscopy (SEM) micrographs show that the particle size of the LiNi_0.5Mn_1.5O₄ powders ranges in the submicronic domain with a narrow grain-size distribution. The substitution of the 3d⁸ metal for Mn in LiNi_0.5Mn_1.5O₄ oxides is beneficial for its charge–discharge cycling performance. For a cut-off voltage of 3.5–4.9 V, the electrochemical capacity of the Li//LiNi_0.5Mn_1.5O₄ cell is ca. 133 mAh/g during the first discharge. Differences and similarities between LiMn₂O₄ and LiNi_0.5Mn_1.5O₄ oxides are discussed.     

Improvement of the first coulomb efficiency and rate performance of Li1.5Ni0.25Mn0.75O2.5 with spinel LiNi0.5Mn1.5O4 doping

Li_1.1Ni_0.25Mn_0.75O_2.3 and Li_1.5Ni_0.25Mn_0.75O_2.5 have been synthesized by co-precipitation method. The effect of the LiNi_0.5Mn_1.5O₄ spinel structure on physical and electrochemical properties is discussed through the characterizations of X-ray diffraction (XRD), scanning electron microscopy, high-resolution transmission electron microscopy, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and electrochemical performance tests. The LiNi_0.5Mn_1.5O₄ spinel structure is detected in the XRD pattern, TEM image, first discharge, and CV curves of the Li_1.1Ni_0.25Mn_0.75O_2.3 electrode. The rate, cyclic performance, and first coulomb efficiency of Li_1.1Ni_0.25Mn_0.75O_2.35 are higher than those of Li_1.5Ni_0.25Mn_0.75O_2.5. The first coulomb efficiencies of Li_1.1Ni_0.25Mn_0.75O_2.3 and Li_1.5Ni_0.25Mn_0.75O_2.5 are 86.2 and 74.7 %, and the capacity retentions are 98.7 and 94.1 % after 50 cycles, respectively. EIS results indicate that the charge-transfer reaction resistance of Li_1.1Ni_0.25Mn_0.75O_2.3 is lower than that of Li_1.5Ni_0.25Mn_0.75O_2.5, which is responsible for the better rate capacity of Li_1.1Ni_0.25Mn_0.75O_2.3.     

Structure and magnetic properties of Ni0.5Zn0.5Mn0.5-xMoxFe1.5O4 ferrites prepared by sol-gel auto-combustion method

A series of Mo doped Ni-Mn-Zn ferrites compounds with the formula Ni_0.5Zn_0.5Mn_0.5-xMo_xFe_1.5O₄ (x = 0, 0.025, 0.05, 0.075 and 0.1) were first synthesized by sol-gel auto-combustion method. The X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), and vibrating sample magnetometer (VSM) analysis were carried out to characterize the microstructural and magnetic properties of ferrites. Rietveld refinement of X-ray diffraction data confirmed the formation of cubic spinel structure and the emergence of FeMoO₄ phase with the substitution of Mo⁶⁺ contents. The grain size increased remarkably due to the formation of the liquid phase. The saturation magnetization (M_s) increased while the coercivity (H_c) decreased from 67.3 to 12.1 Oe due to the decrease of magneto-crystalline anisotropy constant. The initial permeability (μ_i) increased significantly from 34 (x = 0) to 114 (x = 0.075) and later decreased for x = 0.1. In our experiment, Ni_0.5Zn_0.5Mn_0.425Mo_0.075Fe_1.5O₄ ferrite presented the best microstructure and soft magnetic properties.     

Three-dimensionally ordered composite electrode between LiMn2O4 and Li1.5Al0.5Ti1.5(PO4)3

A novel electrode system composed of three-dimensionally ordered macroporous (3DOM) Li_1.5Al_0.5Ti_1.5(PO₄)₃ (LATP) and LiMn₂O₄ was fabricated by the colloidal crystal templating method and sol–gel process. A LATP nanoparticle for the fabrication of 3DOM-LATP was prepared by a sol–gel process. A suspension containing polystyrene (PS) beads and the LATP nanoparticles was filtrated by using a polycarbonate filter to accumulate PS beads and LATP. The accumulated PS beads had a close-packing structure, and the void between PS beads was filled with LATP nanoparticles. 3DOM-LATP was obtained by heat treatment of the accumulated composite. Li–Mn–O sol was injected by a vacuum impregnation process into the macropores of 3DOM-LATP and then was heated to form three-dimensionally ordered composite materials consisting of LiMn₂O₄ and LATP. The formation of the composite between 3DOM-LATP and LiMn₂O₄ were confirmed with scanning electron microscopy and X-ray diffraction method. The prepared composite electrode system exhibited a good electrochemical performance. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

Sonochemical synthesis of LiNi0.5Mn1.5O4 and its electrochemical performance as a cathode material for 5 V Li-ion batteries

LiNi_0.5Mn_1.5O₄ was synthesized as a cathode material for Li-ion batteries by a sonochemical reaction followed by annealing, and was characterized by XRD, SEM, HRTEM and Raman spectroscopy in conjunction with electrochemical measurements. Two samples were prepared by a sonochemical process, one without using glucose (sample-S1) and another with glucose (sample-S2). An initial discharge specific capacity of 130 mA h g⁻¹ is obtained for LiNi_0.5Mn_1.5O₄ at a relatively slow rate of C/10 in galvanostatic charge–discharge cycling. The capacity retention upon 50 cycles at this rate was around 95.4% and 98.9% for sample-S1 and sample-S2, respectively, at 30 °C.     

Effect of temperature on lithium-ion intercalation kinetics of LiMn1.5Ni0.5O4-positive-electrode material

LiMn_1.5Ni_0.5O₄ is synthesized by a sol–gel method and the intercalation kinetics as positive electrode for lithium-ion batteries is investigated by EIS. LiMn_1.5Ni_0.5O₄ particles prepared via sol–gel process possess spinel phase with Fd-3m space group. The charge-transfer resistance, the exchange-current density and the solid-phase diffusion are found as a function of temperature. The apparent activation energy of the exchange current, the charge transfer, and the lithium diffusion in solid phase are also determined, respectively. This result indicates that the effect of the temperature on the cell capacity and the current dependence of the capacity results mainly from the enhancement of the lithium diffusion at elevated temperatures. It can be concluded that LiMn_1.5Ni_0.5O₄ cell has a bad rate cycling performance at elevated temperatures before any modification due to the high diffusion apparent activation energy. The relevant theoretical elucidations thus provide us some useful insights into the design of novel LiMn_1.5Ni_0.5O₄-based positive-electrode materials.     

Enhanced electrochemical performances of layered LiNi0.5Mn0.5O2 as cathode materials by Ru doping for lithium-ion batteries

Ionics - The pristine and Ru-doped LiNi0.5Mn0.5O2 cathode materials are synthesized by a wet chemical method, followed by a high-temperature calcination process. The influence of Ru substitution on...     

The intercalation/deintercalation kinetic studies on the structure-integrated cathode material 0.5Li2MnO3 0.5LiNi0.5Mn0.5O2

A cathode material, 0.5Li₂MnO₃ 0.5LiNi_0.5Mn_0.5O₂, was prepared by citric acid-assisted sol–gel method and its electrochemical performance was investigated. It delivered a charge capacity of 270 mAh g^?1 and a discharge capacity of 189 mAh g^?1 in the first cycle. With the increase of current density from 14 to 28 mA g^?1, the discharge capacity dropped severely to 130 mA g^?1. Obviously, the rate capability of the material was inferior to most of the oxide cathode materials. The diffusion coefficient of this material was calculated to be 6.04?×?10^?12 cm² s^?1 from the results of cyclic voltammetry measurements. Moreover, diffusion coefficients between 3.13?×?10^?12 and 1.22?×?10^?10 cm² s^?1 in the voltage range of 3.8–4.7 V were obtained by capacity intermittent titration technique. This, together with the localized Li₂MnO₃ domains in the crystal structure, may validate the poor rate capability.     

Effects of ultrasound irradiation on Au nanoparticles deposition on carbon-coated LiNi0.5Mn1.5O4 and its performance as a cathode material for Li ion batteries

LiNi_0.5Mn_1.5O₄ (LMNO) has attracted considerable attention as a Li-ion battery cathode material, owing to its high discharge voltage of 4.7 V (vs. Li/Li⁺) and high energy density. However, the electronic conductivity of LMNO is low, resulting in a low discharge capacity at high current density. To overcome this limitation, we deposited Au nanoparticles (NPs), which have a high conductivity and chemical stability at high battery voltages, on carbon-coated LMNO (LMNO/C) using ultrasound irradiation. Consequently, Au NPs that are ∼16 nm in size were deposited on LMNO/C, and ultrasound irradiation was reported to disperse the NPs on LMNO/C more effectively than stirring. Furthermore, the deposition of Au NPs on LMNO/C using ultrasound irradiation improved its electronic conductivity, which is related to an increase in the discharge capacity due to the reduction of Ni⁴⁺ to Ni²⁺ in LMNO/C at a high current density.     

Preparation of TiO2-coated LiMn2O4 by carrier transfer method

The TiO₂-coated LiMn₂O₄ has been prepared by a carrier transfer method and investigated. This novel synthetic method involved the transfer of TiO₂ into the surface of LiMn₂O₄ with Vulcan XC-72 active carbon powders as a dispersant. The X-ray diffraction shows that spinel structure of materials does not change after the coating of TiO₂. The electrochemical performance tests show that the initial discharge capacity of TiO₂-modified LiMn₂O₄ is 111.5 mA h g⁻¹, which is better than that of pristine LiMn₂O₄ (103.8 mA h g⁻¹). The cyclic performance is significantly improved after surface modification. The TiO₂-modified LiMn₂O₄ by a carrier transfer method exhibits better discharge capability and lower resistance.     

Enhanced electrochemical performances of LiNi0.5Co0.2Mn0.3O2 cathode material co-coated by graphene/TiO2

The electrochemical performances of LiNi_0.5Co_0.2Mn_0.3O₂ (NCM523) layered cathode material, such as poor rate capacity and cycling stability caused by undesirable intrinsic conductivity and low rate of lithium ion transportation, are not fairly good especially at elevated rate and cut-off voltage. To improve these properties, in this study, the co-coating layer of graphene and TiO₂ was constructed on NCM523 surface. The graphene/TiO₂ coating layer could effectively prevent hydrofluoric acid (HF) attacks, suppress the side reaction, accelerate the lithium ion diffusion and facilitate the electron migration. The enhancement of cycle performance and rate capacity was contributed to the uniform co-modified surface, interacting each other and thus exhibiting synergistic effects.     

Fabrication and Characterization of Mn0.5Zn0.5Fe2O4 Magnetic Nanofibers

Mn0.5Zn0.5Fe2O4 Magnetic nanofibers were fabricated by calcining electrospun polymer/inorganic composite nanofibers and characterized by thermogravimetric and differential thermal analysis, x-ray diffraction, field emission scanning electron microscopy, high resolution transmission electron microscopy and a vibrating sample magnetometer. The experimental results show that the pure spinel structure is basically formed when the composite nanofibers are calcined at 450°C for 2h. With the increasing calcination temperature, both the saturation magnetization and coercivity of nanofiber samples increase initially along with the growth of Mn0.5Zn0.5Fe2O4 nanocrystals contained in the nanofibers. However, when the calcination temperature reaches 550°C, the saturation magnetization of nanofibers starts to dramatically decrease owing to the formation of the α-Fe2O3 phase at this temperature. The prepared Mn0.5Zn0.5Fe2O4 nanofibers calcined at 500°C for 2h have diameters ranging from 100 to 200nm. Their saturation magnetization and coercivity are 12.37emu/g and 4.81kA/m at room temperature, respectively.     

Magnetic properties of polycrystalline films of CoCr2O4 and CoFe0.5Cr1.5O4 multiferroics

This paper reports on the first study of the magnetic properties of polycrystalline films of CoCr₂O₄ and CoFe_0.5Cr_1.5O₄ multiferroics. The study covered, in particular, magnetization reversal curves and temperature dependences of the magnetization at temperatures ranging from 4.2 to 300 K in magnetic fields of up to 10 kOe. It has been shown that the Curie temperature and the pattern of the temperature dependence of the magnetization depend on the cation composition of the multiferroic. The temperature dependence of the magnetization of polycrystalline CoCr₂O₄ films has revealed an anomaly in the temperature range 10–70 K.     

Submicrocubes and highly oriented assemblies of MnCO3 synthesized by ultrasound agitation method and their thermal transformation to nanoporous Mn2O3

MnCO(3) submicrocubes and highly oriented MnCO(3) nanocrystal assemblies with an ellipsoidal morphology have been successfully prepared by an ultrasonic solution approach. The effect of surfactants of sodium dodecylsulfate (SDS) and aerosol OT (AOT) on the morphology of MnCO(3) was investigated. Highly oriented ellipsoidal assemblies composed of approximately 5 nm MnCO(3) nanocrystals with porous nanostructures were prepared in the presence of SDS. Both sonochemical irradiation and surfactant play an important role in the formation of these highly oriented assemblies. Nanoporous Mn(2)O(3) was obtained by thermal treatment of MnCO(3) at 600 degrees C in air. The shape of MnCO(3) was sustained after thermal transformation to form nanoporous Mn(2)O(3). The products were characterized by X-ray powder diffraction, transmission electron microscopy, selected-area electron diffraction, field emission scanning electron microscopy, thermogravimetric analysis and differential scanning calorimetric analysis.     

Preparation, characterization and electrochemical performance of γ-MnO2 and LiMn2O4 as cathodes for lithium batteries

The spinel LiMn₂O₄ is a very promising cathode material with economical and environmental advantages. LiMn₂O₄ materials have been synthesized by solid state method using γ-MnO₂ as manganese source, and Li₂CO₃ or LiNO₃ as Li sources. γ-MnO₂ is a commercial battery grade electrolytic manganese dioxide (TOSOH-Hellas GH-S) and LiMn₂O₄ samples were synthesized at a calcinations temperature up to 800 °C. γ-MnO₂ and LiMn₂O₄ samples were characterized by X-ray diffraction, thermal and electrochemical measurements. X-ray powder diffraction of as prepared LiMn₂O₄ showed a well-defined highly pure spinel single phase. The electrochemical performance of LiMn₂O₄ and its starting material γ-MnO₂ was evaluated through cyclic voltammetry, galvanostatic (constant current charge-discharge cycling) The electrochemical properties in terms of cycle performance were also discussed. γ-MnO₂ showed fairly high initial capacity of about 200 mAhg⁻¹ but poor cycle performance. LiMn₂O₄ samples showed fairly low initial capacity but good cycle performance.     

A first-principles study on phase transition induced by charge ordering of Mn3+/Mn4+ in spinel LiMn2O4

A first-order transition at 290 K in LiMn₂O₄ with a cubic spinel-type structure is known to degrade the electrochemical performance of the positive electrode of rechargeable lithium-ion batteries. Using first-principles density functional theory (DFT), we confirm that the phase transition is induced by charge-ordering of Mn³⁺/Mn⁴⁺ accompanied by orbital-ordering due to Jahn–Teller distortion, which is in agreement with the previous experimental results of Rodríguez-Carvajal et al. [J. Rodríguez-Carvajal, G. Rousse, C. Masquelier, M. Hervieu, Phys. Rev. Lett. 81 (1998) 4660]. The optimized structure of the low-temperature (LT) phase has orthorhombic symmetry with five distinct crystallographic sites for Mn. The spin integration at each Mn site shows that Mn³⁺ resides at three Mn sites and the remaining two sites are occupied by Mn⁴⁺ ions. Total energy calculations indicate that the LT phase is about 0.23 eV/ LiMn₂O₄ more stable than cubic LiMn₂O₄ (high-temperature phase). The electrochemical Li extraction reaction from the LT phase is also investigated using DFT calculations. The results indicate that the reaction is initially divided into two voltage regions. Electrostatic interactions in the LT phase are calculated using a point charge model, accounting for the features of the electronic configurations and electrochemical reactions.