Enhancement of the electrochemical properties of LiMn2O4 by glycolic acid-assisted sol-gel method

LiMn₂O₄ spinel cathode was synthesized by the sol–gel method by using glycolic acid as a chelating agent. The sample exhibited a pure cubic spinel structure without any impurities in the X-ray diffraction (XRD) patterns. The result of the electrochemical performances on the sample compared to those of electrodes based on LiMn₂O₄ spinel synthesized by solid state. LiMn₂O₄ synthesized by glycolic acid-assisted sol–gel method improves the cycling stability of electrode. The capacity retention of sol–gel-synthesized LiMn₂O₄ was about 90• after 100 cycles between 3.0 and 4.4 V at room temperature. The electrochemical performance of the LiMn₂O₄ (sol–gel) and LiMn₂O₄ (solid state) were investigated under 40• between 3.0 and 4.4 V. XRD results of the cathode material after 50 cycles at 40• revealed that LiMn₂O₄ (sol–gel) could effectively suppress the LiMn₂O₄ dissolving of into electrolyte and resulted in a better stability.     

A novel approach to synthesize lithium ion battery spinel cathode materials

Spinel LiMn₂O₄ and LiMg_0.2Mn_1.8O₄ have been synthesized by a soft chemistry method using citric acid as the chelating agent and acryl amide as the gelling agent. This technique offers better homogeneity, preferred surface morphology, reduced heat treatment conditions, sub-micron-sized particles, and better crystallinity. The synthesized spinel materials are characterized by X-ray diffraction, scanning electron microscopy, cyclic voltammetry, and charge–discharge studies.     

Synthesis and characterization of spinel LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles prepared by high-energy milling and hydrothermal method

Spinel LiMn₂O₄ has been known to be a technologically important, environmental-friendly, and low-cost cathode material used in Li-based rechargeable batteries, and it is also widely available. Nanoparticle spinel LiMn₂O₄ has been synthesized by the top-down, high-energy milling, and hydrothermal methods. SEM images, X-ray diffraction patterns, and neutron high-resolution powder diffraction patterns have confirmed the nanocrystalline nature of the spinel LiMn₂O₄ samples. Raman and Fourier transform infrared (FTIR) measurements show typical absorption and vibration spectra typical for the spinel LiMn₂O₄ showing the formation of various metallic bonds in the sample. The strongest Raman and FTIR signals come from the higher frequency region, with weaker signals appearing in the lower frequency range.     

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.     

Solution synthesis of boron substituted LiMn2O4 spinel oxide for use in lithium rechargeable battery

An attempt has been made to synthesize LiMn₂O₄ spinel and boron substituted LiMn₂O₄ with atomic concentration of boron ranging from 0.01–0.20 and using glutaric acid as a chelating agent. The spinels have been characterized using PXRD, CV and galvanostatic charge-discharge studies. The precursor obtained from the glutaric acid assisted gel was calcined initially at 300 °C for 4 h to obtain the compound and finally at 800 °C for 4 h so as to obtain homogeneity, high degree of purity and crystallinity for better electrochemical performance. This paper suggests that glutaric acid assisted B³⁺ doped (LiB_xMn_2−xO₄) spinel was found to be as an apt candidate with good electrochemical performance for use in lithium battery.     

Improvement of storage performance of LiMn2O4/graphite battery with AlF3-coated LiMn2O4

LiMn₂O₄/graphite batteries using AlF₃-coated LiMn₂O₄ have been fabricated and their electrochemical performance including discharge capacity and cyclic and storage performances have been tested and compared with pristine LiMn₂O₄/graphite batteries. The LiMn₂O₄/graphite battery with AlF₃-coated LiMn₂O₄ shows better capacity (108.5 mAhg^?1), cyclic performance (capacity retention of 92.7 % after 70 cycles), and capacity recovery ratio (98.6 %) than the pristine LiMn₂O₄ battery. X-ray diffraction patterns shows that the spinel structure of AlF₃-coated LiMn₂O₄ can be controlled better than that of pristine LiMn₂O₄ after storage. The improvement in electrochemical performance of the AlF₃-coated LiMn₂O₄/graphite battery is due to the fact that AlF₃ acts as a stabilizer and can protect the oxide structure from damaging during storage, leading to a smaller resistance and polarization after storage.     

Multi-faceted highly crystalline LiMn2O4 and LiNi0.5Mn1.5O4 cathodes synthesized by a novel carbon exo-templating method

LiMn₂O₄ and LiNi_0.5Mn_1.5O₄ powders have been synthesized by a novel cost-effective carbon exo-templating process. It has been observed that controlled nucleation in the pores of highly surface active carbon produces a distinct effect on the powder morphology and crystallinity. Quantitative X-ray phase analyses show single phase spinel structure having Fd3m symmetry for both samples. Field emission electron microscopy reveals particles of size 0.5–1.0 µm with well defined multi-faceted crystals. Cyclic voltammetry results show well separated distinct redox peaks at 4.05/3.92 and 4.17/4.08 V for LiMn₂O₄/Li and 4.91/4.61 V for LiNi_0.5Mn_1.5O₄/Li coin cells indicating good crystallinity and reversibility of the cathodes compared to that of pristine LiMn₂O₄ synthesized by conventional combustion process. The LiMn₂O₄/Li and LiNi_0.5Mn_1.5O₄/Li cells deliver an initial discharge capacity of 110 mA h/g and 122 mA h/g respectively at a current density of 0.05 mA/cm² and when cycled at 0.2 mA/cm², the cells maintain 81% and 96% of their initial discharge capacity respectively even after 20 cycles. On the other hand, at the same current density, LiMn₂O₄ synthesized by conventional combustion process suffers from severe capacity fading (only 37.5% capacity retention after the 25th cycle). The capacity fading rate is found to be very less even at further higher current densities (0.4–0.8 mA/cm²) for both LiMn₂O₄/Li and LiNi_0.5Mn_1.5O₄/Li cells synthesized by the templating process. The present study reveals that high crystallinity along with multi-faceted morphology shows a remarkable enhancement in capacity as well as rate performance of pristine LiMn₂O₄ and its Ni derivative.     

Preparation and characterization of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> nanorod by low heating solid state coordination method

Cathode material LiMn₂O₄ nanorod was prepared by annealing of the mixed precursor which was synthesized by low heating solid state coordination method using lithium acetate, manganese acetate and oxalic acid as starting materials. The structures and morphologies of the LiMn₂O₄ nanorod were investigated as a function of annealing temperature and time. The results showed that all samples in different annealing temperatures and time have the same spinel structure. The higher the annealing temperature is, the more complete the crystal structure forms, and the larger the particle size is. In addition, the electrochemical properties of the LiMn₂O₄nanorod were studied in this paper.     

Novel approach to preparation of LiMn2O4 core/LiNixMn2−xO4 shell composite

Combining two methods, coating and doping, to modify spinel LiMn₂O₄, is a novel approach we used to synthesize active material. First we coated the LiMn₂O₄ particles with the nickel oxide particles by means of homogenous precipitation, and then the nickel oxide-coated LiMn₂O₄ was calcined at 750 °C to form a LiNi_xMn_2−xO₄ shell on the surface of spinel LiMn₂O₄ particles. Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), cyclic voltammetry (CV) and charge-discharge test were performed to characterize the spinel LiMn₂O₄ before and after modification. The experimental results indicated that a spinel LiMn₂O₄ core is surrounded by a LiNi_xMn_2−xO₄ shell. The resulting composite showed excellent electrochemical cycling performance with an average fading rate of 0.014% per cycle. This improved cycle stability is greatly attributed to the suppression of Jahn-Teller distortion on the surface of spinel LiMn₂O₄ particles during cycling.     

Significance of Mg doped LiMn2O4 spinels as attractive 4 V cathode materials for use in lithium batteries

LiMn₂O₄ spinel is one of the most promising cathode materials for lithium-ion batteries because of its cheapness and eco-friendliness. Due to Jahn-Teller distortion, the capacity fades, however, upon repeated cycling. Attempts are being made to improve the cycle life of the spinel by substitution of manganese with other cations. In this paper we report the effect of partial substitution of manganese by Mg²⁺ ions in the LiMn₂O₄ phase. LiMg_yMn_2−yO₄ (y=0 – 0.3) has been synthesized by a thermal method and characterized using XRD, TG/DTA and FTIR. The electrochemical performance is correlated with the dopant concentration.     

Electrochemical behaviour of nano-sized spinel LiMn2O4 and LiAlxMn2−xO4 (x=Al: 0.00-0.40) synthesized via fumaric acid-assisted sol-gel synthesis for use in lithium rechargeable batteries

Pristine spinel LiMn₂O₄ and LiAl_xMn_2−xO₄ (x=Al: 0.00-0.40) with sub-micron sized particles have been synthesized using fumaric acid as chelating agent by sol-gel method. The synthesized samples were subjected to thermogravimetric analysis (TGA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and cyclic voltammetry (CV) and galvanostatic cycling studies. The TGA curve of the gel shows several weight-loss regions stepwise amounting to 55% till 800 °C attributed to the decomposition of the precursors. Calcination to higher temperatures (800 °C) yields pure-phase spinel (LiAl_xMn_2−xO₄), as it is evident from the high-intensity XRD reflections matching to the standard pattern. SEM and TEM studies confirm that the synthesized grains are of uniform regular surface morphology. FT-IR studies show stretching and bending vibration bands of Li-O, Li-Al-Mn-O. LiAl_0.1Mn_1.90O₄ spinel was found to deliver discharge capacity of 139 mA h/g during the first cycle with columbic efficiency of 97%. LiAl_0.1Mn_1.90O₄ spinel exhibits the high cathodic peak current indicating better electrochemical performance. Low doping (x=0.1) of Al is found to be beneficial in stabilizing the spinel structure.     

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.     

Precursor derived LiMn2O4 thin films as ionic conductor

Thin films of spinel LiMn₂O₄ have been fabricated using a metallorganic precursor. Crystalline films have been deposited on Au substrates to exhibit as the cathode in rechargeable thin film lithium batteries. The nucleation and growth of spinel LiMn₂O₄ crystallites were investigated with heat treatment of the deposited thin films. Film capacity density as high as 22 μAh/cm² was measured for LiMn₂O₄. The film heat treated at 700 °C were cycled electrochemically up to 30 cycles against Li metal without any degradation of the capacity. There were neither open area nor amorphous layers which prevent the Li⁺ions transfer at the boundaries in the LiMn₂O₄ thin film. The microscopic study revealed that (111) planes in the two grains directly bonded at the grain boundary which could proceed the lithium ion intercalation or deintercalation smoothly.     

Enhanced cycle ability of spinel LiMn2O4 by controlling the phase purity and structural strain

By applying the annealing step during the solid-state synthesis, well-crystallized spinel LiMn₂O₄ with high phase purity was fabricated. The sensitive effect of heating procedure on the structural and electrochemical properties of LiMn₂O₄ product was investigated. It was found that preheat-treatment-calcinations-annealing process can effectively eliminate the impurity phase. The post-annealing process also leads to a better crystalline and suitable strain for the LiMn₂O₄ product, which contributes to the enhanced cycling performance.     

LiPF6-EC-MPC electrolyte for LiMn2O4 cathode in lithium-ion battery

Methyl propyl carbonate (MPC) is a promising single solvent for lithium-ion battery without addition of ethylene carbonate (EC), but it is unstable upon cycling because of exposure to the spinel LiMn₂O₄ cathode. Thus, we attempted to add EC to MPC in order to form LiPF₆-EC-MPC electrolyte; the effects of solvent ratio and salt concentration on the cycling performance of LiMn₂O₄ cathode were also investigated. The experiments were characterized by conductivity measurements, charge-discharge at a constant current density and voltage–capacity curves at low temperature. To further enhance our understanding of the performance improvement of LiMn₂O₄/Li cells, the electrochemical characterization techniques (such as, LSV, EIS) were performed on these cells. The results show that the ionic conductivity of the electrolyte and the cycling performance of the spinel LiMn₂O₄ cathode have been dramatically enhanced. From the point of view of operation at low temperature (− 20 °C), 1 M LiPF₆ EC/MPC (1/3) electrolyte is highly recommended for spinel LiMn₂O₄ cathode in lithium-ion battery.     

Structural, thermal and morphological studies of magnesium substituted-lithium manganese oxide spinels

Coexistence of two phases having space groups of Fd3m and P4₃32 in the Mg-doped LiMn₂O₄ spinel is being reported for the first time in this article. Mg-doped LiMn₂O₄ powders have been synthesized by sol-gel method using citric acid as a chelating agent. X-ray powder diffraction (XRD) studies show that the crystal structure of LiMg_xMn_2−xO₄ for x<0.25 is a single-phase cubic spinel, which has space group of Fd3m. The cubic spinel structures having space group of Fd3m and P4₃32 are found to coexist in the compound for x=0.25. The structure becomes single-phase cubic spinel with space group P4₃32 for x>0.25. Field emission scanning electron microscopy (FESEM) shows that particle size of various synthesized powders ranges from 100 to 350 nm. Particle size decreases with increase in Mg content. Differential thermal analysis (DTA) and thermogravimetry (TG) studies show an exponential decay relationship between Mg-doping content and the decomposition temperature to form nonstoichiometry (LiMg_xMn_2−xO_4−δ) in air atmosphere. Fourier transform infrared spectroscopy (FTIR) analysis shows increase in the number of vibrational bands with increase in Mg content, which indicates ordering of the ions in the case of ordered spinel structure, and consequent reduction of the space group symmetry from O_h⁷ to O⁷.     

Physical properties of LiMn2O4 spinel prepared at moderate temperature

A moderate-temperature method of preparation of the spinel LiMn₂O₄ was developed around 500 °C. Physical features of the products were identified by X-ray photoelectron spectroscopy, X-ray diffractometry, Raman scattering and FTIR spectroscopy. The electronic conductivity of LiMn₂O₄ has been studied as a function of annealing temperature. The product LiMn₂O₄ is identified as a micron-sized powder and analysis of the local environment is in good accordance with the classical structural model of Fd3m space group. LiMn₂O₄ exhibits an electrical conductivity of 1.9×10⁻⁵ S/cm at room temperature with an activation energy of 0.16 eV which corresponds to an electron hopping mechanism between the two charge states of Mn³⁺ and Mn⁴⁺ ions. A first-order phase transition is observed at 292 K.     

Effect of ultrasonic irradiation on structure and electrochemical properties of LiMn2O4 thin films cathode material for Li-ion micro-batteries

Two kinds of spinel LiMn₂O₄ thin film for lithium ion micro-batteries were successfully prepared on polycrystal Pt substrates by spin coating methods, which were carried out under ultrasonic irradiation (USG) and magnetic stirring (MSG), respectively. The microstructures and electrochemical performance of LiMn₂O₄ thin films were characterized by thermogravimetry analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), and galvanostatic charge-discharge measurements. It was found that the crystalline structure of USG samples grew better than that of the MSG samples. At the same time, higher discharge capacity and better cycle stability were obtained for the LiMn₂O₄ thin films of USG at the current density of 50 μAh/cm² between 3.0 and 4.3 V. The 1st discharge capacity was 57.8 μAh/cm²-μm for USG thin films and 51.7 μAh/cm²-μm for MSG thin films. After 50 cycles, 91.4% and 69% of discharge capacity could be retained respectively, indicating that ultrasonic irradiation condition during spin coating was more suitable for preparing spinel LiMn₂O₄ thin films with better electrode performance for lithium ion micro-batteries.     

Influence of Sm<Superscript>3+</Superscript> ion in structural,morphological, and electrochemical properties of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> synthesized by microwave calcination

LiSm_xMn_2–xO₄ samples were synthesized via co-precipitation technique. The structural properties of the synthesized materials were studied using X-ray diffraction analysis and it confirmed the cubic spinel structure for all the compounds. The lattice parameter of LiMn₂O₄ was observed to be 8.2347 Ǻ and it decreased with Sm³⁺ concentration, due to the shrinkage in cell volume aided by higher binding energy between Sm-O bond. The SEM micrographs were analyzed using Image processing software (Image-J) to ascertain the pore and grain properties. The microwave synthesis had been observed to control the bulk grain formation and had yielded lesser porous and nanoparticles. The particle size distributions obtained through photocross correlation laser diffraction analysis had shown that LiMn₂O₄ with 60 nm and Sm-doped compounds with ∼30 nm, respectively. The cyclic voltammetry studies had revealed the decrease in electrocatalytic behavior in the initial cycle for compounds doped with Sm³⁺ ion. The initial capacities of LiMn₂O₄, LiSm_0.05Mn_1.95O₄ and LiSm_0.10Mn_1.90O₄ substituted compounds were observed to be 134.87 mAhg⁻¹, 132.22 mAhg⁻¹ and 126.41 mAhg⁻¹, respectively. The cells were simulated using 1D model namely Dualfoil5.1 program. The simulated results coincide well with the measured results. The cycle life studies reveal 93% capacity retention of samarium-0.05-doped samples when compared with 78.4% of the LiMn₂O₄.     

Thin aluminum film improving the cycle performance of positive electrode of lithium ion battery

A novel method was investigated to improve the cycle performance of the spinel LiMn₂O₄. It is widely different from the traditional way of modifying LiMn₂O₄ particle with compounds or metals. In our study, instead of coating LiMn₂O₄ particle itself with compounds or metals, first we covered the current collector with the mixture of LiMn₂O₄ particle, conductive agents and binders, and then deposited an aluminum film onto it by vacuum evaporation technique. Both of the pristine electrode and the modified one were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), and charge-discharge tests. The results of SEM and XRD demonstrate that the aluminum film was formed successfully onto the positive electrode. And the charge-discharge tests show that the capacity retention of pristine electrode and modified one are 63.7% and 93.5% at C/2 rate in the voltage range of 3.5-4.3 V after 200 cycles, respectively. The modified electrode also shows better rate capability in comparison with the pristine one. The improved cycling stability is attributed to the minimizing of Mn dissolution into electrolyte solution and the good electronic conductivity of deposited aluminum film.