Preparation and electrochemical properties of LiMn2O4 by the microwave-assisted rheological phase method

Pure-phase and well-crystallized spinel LiMn₂O₄ powders as cathode materials for lithium-ion batteries were successfully synthesized by a new simple microwave-assisted rheological phase method, which was a timesaving and efficient method. The physical properties of the as-synthesized samples compared with the pristine LiMn₂O₄ obtained from the rheological phase method were investigated by thermogravimetry analysis (TGA), X-ray diffraction (XRD) and scanning electronic microscope (SEM). The as-prepared powders were used as positive materials for lithium-ion battery, whose charge/discharge properties and cycle performance were examined in detail. The powders resulting from the microwave-assisted rheological phase method were pure, spinel structure LiMn₂O₄ particles of regular shapes with distribution uniformly, and exhibited promising electrochemical properties for battery. Furthermore, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were employed to characterize the reactions of Li-ion insertion into and extraction from LiMn₂O₄ electrode.     

Electrochemical performance of single crystalline spinel LiMn2O4 nanowires in an aqueous LiNO3 solution

Single crystalline cubic spinel LiMn₂O₄ nanowires were synthesized by hydrothermal method and the precursor calcinations. The phase structures and morphologies were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and high-resolution transmission electron microscopy (HRTEM). Galvanostatic charging/discharging cycles of as-prepared LiMn₂O₄ nanowires were performed in an aqueous LiNO₃ solution. The initial discharge capacity of LiMn₂O₄ nanowires was 110 mAh g⁻¹, and the discharge capacity was still above 100 mAh g⁻¹ after 56 cycles at 10C-rate, and then 72 mAh g⁻¹ was registered after 130 cycles. This is the first report of a successful use of single crystalline spinel LiMn₂O₄ nanowire as cathode material for the aqueous rechargeable lithium battery (ARLB).     

All-solid-state lithium battery with a three-dimensionally ordered Li1.5Al0.5Ti1.5(PO4)3 electrode

To fabricate all-solid-state Li batteries using three-dimensionally ordered macroporous Li_1.5Al_0.5Ti_1.5(PO₄)₃ (3DOM LATP) electrodes, the compatibilities of two anode materials (Li₄Mn₅O₁₂ and Li₄Ti₅O₁₂) with a LATP solid electrolyte were tested. Pure Li₄Ti₅O₁₂ with high crystallinity was not obtained because of the formation of a TiO₂ impurity phase. Li₄Mn₅O₁₂ with high crystallinity was produced without an impurity phase, suggesting that Li₄Mn₅O₁₂ is a better anode material for the LATP system. A Li₄Mn₅O₁₂/3DOM LATP composite anode was fabricated by the colloidal crystal templating method and a sol-gel process. Reversible Li insertion into the fabricated Li₄Mn₅O₁₂/3DOM LATP anode was observed, and its discharge capacity was measured to be 27 mA h g⁻¹. An all-solid-state battery composed of LiMn₂O₄/3DOM LATP cathode, Li₄Mn₅O₁₂/3DOM LATP anode, and a polymer electrolyte was fabricated and shown to operate successfully. It had a potential plateau that corresponds to the potential difference expected from the intrinsic redox potentials of LiMn₂O₄ and Li₄Mn₅O₁₂. The discharge capacity of the all-solid-state battery was 480 μA h cm⁻².     

Synthesis and electrochemical properties of LiAl0.05Mn1.95O4 by the ultrasonic assisted rheological phase method

Pure-phase and well-crystallized spinel LiAl_0.05Mn_1.95O₄ powders were successfully synthesized by a simple ultrasonic assisted rheological phase (UARP) method. The structure and morphology properties of this as-prepared powder compared with the pristine LiMn₂O₄ and LiAl_0.05Mn_1.95O₄ obtained from the solid-state reaction (SSR) method were investigated by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical properties focused on the LiAl_0.05Mn_1.95O₄ by this new method have also been investigated in detail. According to these tests results, it is obviously to see that the newly prepared sample delivers a relatively high initial discharge capacity of 111.6 mAh g⁻¹, presents excellent rate capability and reversibility, and shows good cycling stability with capacity retention of 90.6% after 70 cycles. Meanwhile, the electrochemical impedance spectroscopy (EIS) investigations were employed to study the electrochemical process of Li⁺ ions with the synthesized LiAl_0.05Mn_1.95O₄ electrode in detail.     

Preparation and electrochemical performance of composite oxide of alpha manganese dioxide and Li-Mn-O spinel

Nano-sized composite powder which consisted of two manganese-based oxides, alpha manganese dioxide (α-MnO₂) and spinel Li-Mn-O, was successfully formed by intergrowth of the spinel phase inside α-MnO₂. This composite oxide was synthesized by precipitation and heat treatment in air; α-manganese dioxide powder was firstly prepared by oxidative precipitation of Mn(II) with K₂S₂O₈ in an aqueous solution, and then a mixture of the obtained manganese oxide powder and LiOH methanol solution was heat-treated in air. Electron microscopy and diffraction observations confirmed that the manganese oxide composite consisted of nano-sized grains of the spinel LiMn₂O₄ and α-MnO₂ phases. It was found that this α-MnO₂/spinel LiMn₂O₄ composite electrode exhibited highly reversible lithium insertion compared to the pristine α-MnO₂ and conventional LiMn₂O₄, that is, the composite demonstrated high discharge capacity of 148 mAh g⁻¹ as a cathode material of lithium cells in the potential range of 2.5-4.3 V with no significant capacity fading. It was thought that the intimately mixing of two oxides on a nanometer scale helped to maintain structural integrity on charge-discharge cycling, which leads to excellent capacity retention for both of the spinel and alpha-type manganese oxide.     

Hydrothermal synthesis of LiMn2O4/C composite as a cathode for rechargeable lithium-ion battery with excellent rate capability

A spinel LiMn₂O₄/C composite was synthesized by hydrothermally treating a precursor of manganese oxide/carbon (MO/C) composite in 0.1 M LiOH solution at 180 °C for 24 h, where the precursor was prepared by reducing potassium permanganate with acetylene black (AB). The AB in the precursor serves as the reducing agent to synthesize the LiMn₂O₄ during the hydrothermal process; the excess of AB remains in the hydrothermal product, forming the LiMn₂O₄/C composite, where the remaining AB helps to improve the electronic conductivity of the composite. The contact between LiMn₂O₄ and C in our composite is better than that in the physically mixed LiMn₂O₄/C material. The electrochemical performance of the LiMn₂O₄/C composite was investigated; the material delivered a high capacity of 83 mAh g⁻¹ and remained 92% of its initial capacity after 200 cycles at a current density of 2 A g⁻¹, indicating its excellent rate capability as well as good cyclic performance.     

Conventional- and microwave-hydrothermal synthesis of LiMn2O4: Effect of synthesis on electrochemical energy storage performances

The LiMn₂O₄ electrode materials were synthesized by the conventional-hydrothermal and microwave-hydrothermal methods. The electrochemical performances of LiMn₂O₄ were studied as supercapacitors in LiNO₃ electrolyte and lithium-ion battery cathodes. The microwave-hydrothermal method can synthesize LiMn₂O₄ electrode materials with reversible electrochemical reaction in a short reaction time and low reaction temperature than conventional-hydrothermal route. The capacitance of LiMn₂O₄ electrode increased with increasing crystallization time in conventional-hydrothermal route. The results showed that LiMn₂O₄ supercapacitors had similar discharge capacity and potential window (1.2 V) as that of ordinary lithium-ion battery cathodes. In LiNO₃ aqueous electrolyte, the reaction kinetics of LiMn₂O₄ supercapacitors was very fast. Even, at current densities of 1 A/g and 5 A/g, aqueous electrolyte gave good capacity compared with that in organic electrolyte at a current density of 0.05 A/g.     

Studies of structure and cycleability of LiMn2O4 and LiNd0.01Mn1.99O4 as cathode for Li-ion batteries

Lithium manganese oxides LiMn₂O₄ and rare earth elements doped LiNd_0.01Mn_1.99O₄ were synthesized by microwave method. The structure and the electrochemical performances of the samples were characterized. XRD data shows both samples exhibit the same pure spinel phase. But due to the introduction of Nd³⁺ ion into the unit cell, the lattice parameter of the Nd-doped spinel was larger than that of the undoped one. The two samples had a similar morphology including small particle size and homogeneous particle distribution as tested by SEM. The cyclic voltammmetry and constant-current charge-discharge tested that Nd-doped spinel displayed a better reversibility and cycleability.     

Nanorod-assembled spinel Li1.05Mn1.95O4 rods with a central tunnel along the rod-axis for high rate capability of rechargeable lithium-ion batteries

Nanorod-assembled spinel Li_1.05Mn_1.95O₄ rods with a central tunnel along the rod-axis were synthesized using highly crystalline β-MnO₂ rods as self-templates. The synthesized spinel Li_1.05Mn_1.95O₄ is an assembly of several single crystal-like nanorods with an average diameter and length of 100 and 400 nm, respectively, which was determined by microstructural Rietveld refinement using the synchrotron powder XRD data. Galvanostatic battery testing showed that central-tunneled and nanorod-assembled Li_1.05Mn_1.95O₄ rods have a high charge storage capacity at high current densities in comparison with those of the spinel rods without a tunnel structure and commercial powders. Moreover, a capacity retention value of ∼81% was observed at the end of 100 cycles at a current of 250 mAh g⁻¹.     

Synthesis and electrochemical characterization of nano-CeO2-coated nanostructure LiMn2O4 cathode materials for rechargeable lithium batteries

LiMn₂O₄ spinel cathode materials were coated with 0.5, 1.0, and 1.5 wt.% CeO₂ by a polymeric process, followed by calcination at 850 °C for 6 h in air. The surface-coated LiMn₂O₄ cathode materials were physically characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron microscopy (XPS). XRD patterns of CeO₂-coated LiMn₂O₄ revealed that the coating did not affect the crystal structure or the Fd3m space group of the cathode materials compared to uncoated LiMn₂O₄. The surface morphology and particle agglomeration were investigated using SEM, TEM image showed a compact coating layer on the surface of the core materials that had average thickness of about 20 nm. The XPS data illustrated that the CeO₂ completely coated the surface of the LiMn₂O₄ core cathode materials. The galvanostatic charge and discharge of the uncoated and CeO₂-coated LiMn₂O₄ cathode materials were measured in the potential range of 3.0-4.5 V (0.5 C rate) at 30 °C and 60 °C. Among them, the 1.0 wt.% of CeO₂-coated spinel LiMn₂O₄ cathode satisfies the structural stability, high reversible capacity and excellent electrochemical performances of rechargeable lithium batteries.     

Enhanced cycling stability of LiMn2O4 cathode by amorphous FePO4 coating

The cycling performance of LiMn₂O₄ at room and elevated temperatures is improved by FePO₄ modification through chemical deposition method. The pristine and FePO₄-coated LiMn₂O₄ materials are characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy. Their cycling performances are thoroughly investigated and compared. The 3 wt.% FePO₄-coated LiMn₂O₄ exhibits capacity losses of only 32% and 34% at room temperature and 55 °C, respectively, after 80 cycles, much better than those of the pristine material, 55% and 72%. The cyclic voltammograms at 55 °C reveal that the improvement in the cycling performance of FePO₄-coated LiMn₂O₄ electrodes can be attributed to the stabilization of spinel structures. The separation of FePO₄ between active materials and electrolyte and its interaction with SEI (solid electrolyte interphase) film are believed to account for the improved performances.     

Crystal structure studies of thermally aged LiCoO2 and LiMn2O4 cathodes

LiCoO₂ and LiMn₂O₄ cathodes were studied by X-ray diffractometry (XRD) and electron diffraction after ageing in the charged state at elevated temperature. Some cathodes were stopped at different times during ageing and XRD measurements were taken to monitor changes in the crystal structure over ageing time. The results indicate that Li-ions intercalate into the cathodes lattice during ageing thus decreasing the available discharge capacity. Analysis of electron diffraction patterns of LiCoO₂ and LiMn₂O₄ retrieved from the cathodes after ageing shows that irreversible crystallographic transformations have taken place in both electrodes. Dark field imaging illustrates that LiCoO₂ forms a layer of spinel phase on its surface. In LiMn₂O₄ a tetragonal distorted spinel is observed when the cathode has been in the 3 V regime for considerable length of time.     

A comparative electrochemical study of LiMn2O4 spinel thin-film and porous laminate

Novel Electrostatic Spray Deposition (ESD) technique was used to fabricate LiMn₂O₄ spinel thin-films. Cyclic voltammograms of both the ESD and porous laminate films show the double peaks in the 4.0 V range characteristic of the LiMn₂O₄ spinel materials. The porous laminates exhibit two semicircles in the impedance spectra while the ESD films show only one single semicircle. The diffusion time constant in the laminate films was typically one order of magnitude larger than that in the ESD thin-films. The apparent lithium-ion chemical diffusion coefficient in LiMn₂O₄ was found to be of the order of 10⁻⁹ cm²/s for both the porous laminate film and the ESD films despite the difference in the diffusion time constants.     

Electrochemical and ex situ XRD studies of a LiMn1.5Ni0.5O4 high-voltage cathode material

Sub-micro spinel-structured LiMn_1.5Ni_0.5O₄ material was prepared by a spray-drying method. The electrochemical properties of LiMn_1.5Ni_0.5O₄ were investigated using Li ion model cells, Li/LiPF₆ (EC + DMC)/LiMn_1.5Ni_0.5O₄. It was found that the first reversible capacity was about 132 mAh g⁻¹ in the voltage range of 3.60-4.95 V. Ex situ X-ray diffraction (XRD) analysis had been used to characterize the first charge/discharge process of the LiMn_1.5Ni_0.5O₄ electrode. The result suggested that the material configuration maintained invariability. At room temperature, on cycling in high-voltage range (4.50-4.95 V) and low-voltage range (3.60-4.50 V), the discharge capacity of the material was about 100 and 25 mAh g⁻¹, respectively, and the spinel LiMn_1.5Ni_0.5O₄ exhibited good cycle ability in both voltage ranges. However, at high temperature, the material showed different electrochemical characteristics. Excellent electrochemical performance and low material cost make this spinel compound an attractive cathode for advanced lithium ion batteries.     

Nano-crystalline LiNi0.5Mn1.5O4 synthesized by emulsion drying method

LiNi_0.5Mn_1.5O₄ spinel has been prepared by an emulsion drying method which can intermix cations very homogeneously at the atomic scale. When the emulsion-dried precursor was fired at 750 °C for 24 h, the observed particle of the LiNi_0.5Mn_1.5O₄ was nano-crystallite, being about 50 nm in diameter. The Rietveld refinement result clearly exhibited that the cubic spinel phase was successfully formed without any secondary phases, indicating that Li and transition metal cations occupied the 8a and 16d sites of the Fd3m structure, respectively. Li deintercalation from the spinel framework brings about a shift in the XRD peak toward higher angles and a peak splitting in the composition range δ=0-0.2 in Li_δNi_0.5Mn_1.5O₄, implying that the host structure is progressively oxidized from Ni²⁺ to Ni⁴⁺ and accompanied by a two phase reaction. The sample calcined at 750 °C for 24 h showed the best cyclability upon cycling due probably to better crystallinity and a smaller particle size. We suggest that this material can be used as a 4.5 V cathode material for Li-ion battery.     

Synthesis of spherical spinel LiMn2O4 with commercial manganese carbonate

Spherical spinel LiMn₂O₄ particles were successfully synthesized from a mixture of manganese compounds containing commercial manganese carbonate by sintering of the spray-dried precursor. Different preparation routes were investigated to improve the tap density and to enhance the electrochemical performance of LiMn₂O₄. The structure and morphology of the LiMn₂O₄ particles were confirmed by X-ray diffraction (XRD) and scanning electron microscopy. The results showed that hollow spherical LiMn₂O₄ particles could be obtained when only commercial MnCO₃ was used as the manganese source. These particles had a low tap density (ca.0.8 g/cm³). Perfect micron-sized spherical LiMn₂O₄ particles with good electrochemical performance were obtained by spray-drying a slurry composed of MnCO₃, Mn(CH₃CHOO)₂ and LiOH, followed by a dynamic sintering process and a stationary sintering process. The as-prepared spherical LiMn₂O₄ particles comprised hundreds of nanosize crystal grains and had a high tap density(ca. 1.4 g/cm³). The galvanostatic charge-discharge measurements indicated that the spherical LiMn₂O₄ particles had an initial capacity of 121 mAh/g between 3.0 and 4.2 V at 0.2 C rate and still delivered a reversible capacity of 112 mAh/g at 2 C rate. The retention of capacity after 50 cycles was still 96% of its initial capacity at 0.2 C. All the results showed that the as-prepared spherical LiMn₂O₄ particles had an excellent electrochemical performances. The methods we used for preparing spherical LiMn₂O₄ are energy-saving and suitable for industrial application.     

Effects of precursor treatment with reductant or oxidant on the structure and electrochemical properties of LiNi0.5Mn1.5O4

LiNi_0.5Mn_1.5O₄, a lithium-ion battery cathode material, is prepared using co-precipitation via a two-step drying method with Ni-Mn mixed hydroxide as the precursor. This study examines the effects of precursor pretreatment with hydrazine (a reductant) or with H₂O₂ (an oxidant) in solutions of NiSO₄ and MnSO₄. The results indicate substantial differences in the structure and electrochemical properties of LiNi_0.5Mn_1.5O₄ depending on whether the precursor is pretreated with reductant or oxidant. For the hydrazine-treated precursor, the synthesized LiNi_0.5Mn_1.5O₄ has a very pure spinel phase and an ordered, octahedral crystal morphology (ca. 100-300 nm). In contrast, the material synthesized using the H₂O₂-treated precursor shows numerous impurity phases (Na_0.7MnO_2.05) with a layer-by-layer crystal structure. The control sample (prepared without precursor pretreatment) maintains an octahedral structure but still retains a few impurity phases of Na_0.7MnO_2.05. The electrochemical results show that LiNi_0.5Mn_1.5O₄ synthesized using a hydrazine-treated precursor has a higher specific capacity (especially under high discharge current) and a higher cyclic life than the control sample, whereas the sample using H₂O₂-treated precursor shows almost no special capacity due to changes in crystal structure.     

Synthesis and characterization of mesostructured tungsten nitride by using tungstic acid as the precursor

Mesostructured tungsten nitride was firstly prepared from tungstic acid via the temperature programmed reaction with ammonia. The N₂ adsorption isotherm of as-synthesized tungsten nitride was of type IV with a type H-3 hysteresis loop. BJH pore size distribution was of bimodal distribution (2.5 and 3.5 nm), among which the latter was the main channel of tungsten nitride. The surface area of as-synthesized tungsten nitride was up to 89 m² g⁻¹. XRD pattern showed that the crystal phase of the product was β-W₂N. The effect of synthesis parameters on the surface area of tungsten nitride was investigated extensively. The nitridation mechanism was investigated by in-situ XRD and N₂ adsorption analysis. It was found that H₂WO₄ was initially transformed into WO₃ by eliminating the axial water molecules, and WO₃ retained the layered and porous structure of H₂WO₄. Below 773 K, WO₃ was just partially reduced to W₂₀O₅₈ and W₂₀O₄₀. Above 773 K, β-W₂N phase could be detected. It indicated that during nitridation, WO₃ was gradually reduced and then the homogeneous substitution of oxygen vacancies in the reduced oxides with nitrogen atoms occurred. Based on the experimental results, a reduction-nitridation mechanism was firstly proposed.     

Submicro-sized LiMn2O4 prepared by a sol–gel, spray-drying method

Submicro-sized LiMn₂O₄ powders were produced by a sol–gel, spray-drying method in which a brown gel precursor was prepared via the reaction of LiOH alkaline solution with 1 M Mn(CH₃COO)₂. The gel precursor was then transferred into a dry precursor powder via a spray-dry process. After heating treatment the spinel LiMn₂O₄ powder was obtained. The composition and the crystal size of the samples were strongly affected by the spray speed in the drying process and the heating temperature. The structure and the morphology of LiMn₂O₄ powder were investigated by DTA, TGA, IR, XRD and SEM methods. It was discovered that submicro-sized LiMn₂O₄ powder could be formed under the conditions of rotating spray speed of 15 000 rpm and syntheses temperature of 700 °C. The electrochemical properties of LiMn₂O₄ samples in 1 M LiPF₆, EC:DMC = 1:1 solution were tested by measuring the voltammograms and charge–discharge curves. The submicro-sized LiMn₂O₄ sample made at 700 °C has a capacity of 128 mAh g^–1 and good cycle stability for Li⁺ intercalation reaction. This method may be applied to the industrial-scale production of superfine LiMn₂O₄ powder for use in lithium ion batteries.     

Molten salt synthesis of LiNi0.5Mn1.5O4 spinel for 5 V class cathode material of Li-ion secondary battery

Well-ordered high crystalline LiNi_0.5Mn_1.5O₄ spinel has been readily synthesized by a molten salt method using a mixture of LiCl and LiOH salts. Synthetic variables on the synthesis of LiNi_0.5Mn_1.5O₄, such as synthetic atmosphere, LiCl salt amount, synthetic temperature, and synthetic time, were intensively investigated. X-ray diffraction (XRD) patterns and scanning electron microscopic (SEM) images showed that LiNi_0.5Mn_1.5O₄ synthesized at 900 and 950 °C have cubic spinel structure () with clear octahedral dimension. LiNi_0.5Mn_1.5O₄ spinel phase began to decompose at around 1000 °C accompanied with structural and morphological degradation. LiNi_0.5Mn_1.5O₄ powders synthesized at 900 °C for 3 h delivered an initial discharge capacity of 139 mAh/g with excellent capacity retention rate more than 99% after 50 cycles.