ZnO-coated LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> cathode material for lithium-ion batteries synthesized by a combustion method

ZnO-coated LiMn₂O₄ cathode materials were prepared by a combustion method using glucose as fuel. The phase structures, size of particles, morphology, and electrochemical performance of pristine and ZnO-coated LiMn₂O₄ powders are studied in detail by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), galvanostatic charge-discharge test, and X-ray photoelectron spectroscopy (XPS). XRD patterns indicated that surface-modified ZnO have no obvious effect on the bulk structure of the LiMn₂O₄. TEM and XPS proved ZnO formation on the surface of the LiMn₂O₄ particles. Galvanostatic charge/discharge test and rate performance showed that the ZnO coating could improve the capacity and cycling performance of LiMn₂O₄. The 2 wt% ZnO-coated LiMn₂O₄ sample exhibited an initial discharge capacity of 112.8 mAh g^?1 with a capacity retention of 84.1 % after 500 cycles at 0.5 C. Besides, a good rate capability at different current densities from 0.5 to 5.0 C can be acquired. CV and EIS measurements showed that the ZnO coating effectively reduced the impacts of polarization and charge transfer resistance upon cycling.     

Ultrathin surface coatings to enhance cycling stability of LiMn2O4 cathode in lithium-ion batteries

Spinel LiMn₂O₄ suffers from severe dissolution when used as a cathode material in rechargeable Li-ion batteries. To enhance the cycling stability of LiMn₂O₄, we use the atomic layer deposition (ALD) method to deposit ultrathin and highly conformal Al₂O₃ coatings (as thin as 0.6–1.2 nm) onto LiMn₂O₄ cathodes with precise thickness control at atomic scale. Both bare and ALD-coated cathodes are cycled at a specific current of 300 mA g^?1 (2.5 C) in a potential range of 3.4–4.5 V (vs. Li/Li⁺). All ALD-coated cathodes exhibit significantly improved cycleability compared to bare cathodes. Particularly, the cathode coated with six Al₂O₃ ALD layers (0.9 nm thick) shows the best cycling performance, delivering an initial capacity of 101.5 mA h?g^?1 and a final capacity of 96.5 mA h?g^?1 after 100 cycles, while bare cathode delivers an initial capacity of 100.6 mA h?g^?1 and a final capacity of only 78.6 mA h?g^?1. Such enhanced electrochemical performances of ALD-coated cathodes are ascribed to the high-quality ALD oxide coatings that are highly conformal, dense, and complete, and thus protect active material from severe dissolution into electrolytes. Besides, cycling performances of coated cathodes can be easily optimized by accurately tuning coating thickness via varying ALD growth cycles.     

The optimized preparation and electrochemical properties of LiMn1.95Co0.05O4 and Al2O3-coated LiMn1.95Co0.05O4

Cathode material LiMn_1.95Co_0.05O₄ for lithium ion battery was synthesized via solid state reaction, and calcination temperature and time were investigated, respectively. Thermogravimetry (TG) and differential thermal analysis (DTA) measurements were utilized to determine the calcination temperature of precursor sample. The optimized calcination temperature and time are 850 °C and 15 h. The surface of LiMn_1.95Co_0.05O₄ cathode is coated using Al₂O₃ coating materials. The phase structures, surface morphologies, and element types of the prepared LiMn_1.95Co_0.05O₄ and Al₂O₃-coated LiMn_1.95 Co_0.05O₄ were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and energy spectrum analysis (EDS). The 0.5 wt% Al₂O₃-coated compound exhibited better specific capacity and capacity retention than bare sample. The initial discharge capacity was 140.9 mAh/g and capacity retention was 96.7 % after 10 cycles at 0.1 C. Such enhancements are attributed to the presence of a stable Al₂O₃ layer which acts as the interfacial stabilizer on the surface of LiMn_1.95Co_0.05O₄.     

Low content Ni and Cr co-doped LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> with enhanced capacity retention

Nanoparticles of the pure and Ni–Cr co-doped lithium manganese oxides Li[Ni_xCr_yMn_2-x-y]O₄ (x = y = 0.01–0.05) have been synthesized by sol–gel method using citric acid as a chelating agent. The effect of low-content doping was noted reflecting the faster ionic movement in the cathode material. The phase structure and morphology of the materials are characterized by XRD, FTIR, SEM and TEM. Electrochemical and impedance measurements established that low-content Ni–Cr substitution substantially improves the structural stability and high rate cycling performance of LiMn₂O₄. Among all the investigated compositions, LiNi_0.01Cr_0.01Mn_1.98O₄ demonstrated the best electrochemical performance. At a substantially high current rate of 5 C, 82% of the initial discharge capacity at 0.1 C is retained. Remarkably, after deep cycling at high rates, a discharge capacity of 104 mAhg^?1 is resumed upon reducing the current rate to 0.1 C which is 91% of the specific capacity in the first cycle.     

Effect of heptamethyldisilazane on the electrochemical performance of LiMn2O4/Li

The effect of heptamethyldisilazane as an electrolyte stabilizer on the cycling performance of a LiMn₂O₄/Li cell at different rates at 30 °C and the storage performance at 60 °C is investigated systematically based on conductivity test, linear sweep voltage, electrochemical impedance spectroscopy, scanning electron microscopy, X-ray diffraction, and charge–discharge measurements. The results show that heptamethyldisilazane added into the LiPF₆-based electrolyte can increase the stability of the original electrolyte; coulomb efficiency, the initial discharge capacity, and cycling performance at different rates in a sense, meanwhile, improve the storage performance at elevated temperature, although the C-rate performance of the cell is a little worse than that without heptamethyldisilazane in the electrolyte. When the LiMn₂O₄/Li cell with heptamethyldisilazane in the LiPF₆-based electrolyte stored at 60 °C for a week cycles 300 times, the capacity retention is up to 91.18 %, which is much higher than that (87.18 %) without the additive in the electrolyte. This is mainly due to the lower solid electrolyte interface resistance (R _f) in the cell, followed by the better morphology and structure of the cathode after storage at 60 °C for a week compared with the LiMn₂O₄/Li cell without heptamethyldisilazane.     

Structure and electrochemical performance of LiV x Mn2 − x O4 (0 ≤ x ≤ 0.20) cathode materials for rechargeable lithium ion batteries

LiMn₂O₄ and vanadium-substituted LiV _x Mn_2???x O₄ (x?=?0.05, 0.10 0.15 and 0.20) cathode materials were synthesized by sol–gel method using aqueous solutions of metal nitrates and tartaric acid as chelating agent at 600 °C for 10 h. The structure and electrochemical properties of the synthesized materials were characterized by using X-ray diffraction, SEM, TEM and charge–discharge studies. X-ray powder diffraction analysis was changed in lattice parameters with increasing vanadium content suggesting the occupation of the substituent within LiMn₂O₄ interlayer spacing. TEM and SEM analyses show that LiV_0.15Mn_1.85O₄ has a smaller particle size and more regular morphological structure with narrow size distribution than LiMn₂O₄. It is concluded that the structural stability and cycle life improvement were due to many factors like better crystallinity, smaller particle size and uniform distribution compared to the LiMn₂O₄ cathode material. The LiV_0.15Mn_1.85O₄ cathode material has improved the structural stability and excellent electrochemical performances of the rechargeable lithium ion batteries.     

Surfactant-assisted synthesis of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> particles as high-rate and long-life cathode materials for lithium-ion batteries

Herein, we reported the synthesis of uniform LiMn₂O₄ submicroparticles by surfactant-assisted preparation of spherical MnCO₃ precursor followed by solid-state reaction. Polyethylene glycol (Mw = 1000) was used as surfactant to control the morphology and size of the MnCO₃ precursor as well as the MnO₂ intermediate and LiMn₂O₄ product. The influence of particle size, homogeneity, and crystallinity on the electrochemical performance of LiMn₂O₄ was intensively investigated. The test results indicate that the LiMn₂O₄ sample using polyethylene glycol with weight as 10% of reactants shows the best rate capability and long-term cyclability. Due to the homogeneous particles with the average size of ca. 250 nm and high crystallinity, the discharge capacities are as high as 125, 118, 114, and 100 mAh g^?1 at 1, 10, 20, and 50 C rates, respectively, along with high capacity retention of 74% after 1000 cycles at 20 C.     

Lithium polyacrylate-coated LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> cathode materials with excellent performance for lithium ion batteries

A novel facile approach to coat LiMn₂O₄ by lithium polyacrylate (PAALi) is demonstrated. The PAALi-coated LiMn₂O₄ (LMO@2%PAALi) and LiMn₂O₄ (LMO) are characterized by charge–discharge tests, X-ray diffraction (XRD), PAALi dissolving experiment, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TG), and inductively coupled plasma optical emission spectrometer (ICP-OES). XRD and FTIR analyses indicate that there are no clear differences between LMO@2%PAALi and LMO. PAALi dissolving experiment indicates that PAALi is indissolvable in LiPF₆-EC/DMC/EMC electrolyte. TEM results reveal that LiMn₂O₄ particles are coated by PAALi. ICP-OES results indicate that this stable PAALi coating can prevent the Mn ions dissolving from active LiMn₂O₄ materials and then the stability of LiMn₂O₄ crystals in electrolyte are greatly enhanced. These unique features ensure that LMO@2%PAALi possesses much better rate performance, higher discharge capacity, better cycling performance, and lower charge transfer resistance over LMO. The discharge capacity of LMO@2%PAALi at 0.2 C reaches up to 127.2 mAh g^?1 at room temperature.     

Investigation on the storage performance of LiMn2O4 at elevated temperature with the mixture of electrolyte stabilizer

In order to investigate the effect of different electrolytes of LiPF₆-based and LiPF₆-based with the mixed additives of ethanolamine and heptamethyldisilazane on the storage performance of LiMn₂O₄, the commercial LiMn₂O₄ are added into these different electrolytes for storing deliberately at 60 °C in air for 4 h. The results show that the electrolyte with additives can prevent LiMn₂O₄ from being eroded by HF to a certain extent, and improve the storage performance of the material. The initial discharge capacities are 97.7 and 88.4 mAh g^?1 at 0.1 and 1?C, respectively, which are much higher than that 84.4 and 63.6 mAh?g^?1 of LiMn₂O₄ stored in the electrolyte without additives. Moreover, the former LiMn₂O₄ retains 89.1 % of its initial discharge capacity at 1?C after 150 cycles, while this is not up to 84 % for the latter.     

Improvement of cycling stability of LiMn2O4 cathode by Fe2O3 surface modification for Li-ion battery

The surface of spinel LiMn₂O₄ was modified with Fe₂O₃ (1.0, 2.0, 3.0, 4.0, and 5.0 wt%) by a simple sol-gel method to improve its electrochemical performance at room temperature. Compared with bare LiMn₂O₄, surface modification improved cycling stability of the material. Among the surface-modified cathode materials, the 3.0- and 4.0-wt% surface-modified cathodes have lesser capacity loss than the others. While the bare LiMn₂O₄ showed 25.4 % capacity loss in 70 cycles at room temperature, 3.0 and 4.0 wt% of Fe₂O₃-modified LiMn₂O₄ only exhibited the capacity loss of 2.6 and 2.3 % in 70 cycles at room temperature, respectively. The structure and phase were identified with X-ray diffractometer along with the lattice constant calculated by a Win-Metric program.     

Fabrication of urchin-like NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript> microspheres assembled by using SDS as soft template for anode materials of Lithium-ion batteries

In this paper, the urchin-like NiCo₂O₄ microspheres assembled by using sodium dodecyl sulfate (SDS) as soft template are successfully fabricated by a facile procedure including microemulsion-solvothermal reaction and subsequent calcination at 400 °C for 4 h. The structure and morphology of synthesized NiCo₂O₄ particles are investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It has been clearly revealed that the prepared three-dimensional urchin-like NiCo₂O₄ microspheres are constituted by one-dimension nanowires. As it is applied to anode for lithium-ion batteries (LIBs), the initial coulombic efficiency is up to 75.7%, and the specific reversible capacity retains up to 1034.2 mAh/g even after 40 cycles at a current density of 100 mA/g. Furthermore, as the current density gradually increases to 800 mA/g, it still delivers the reversible capacity of 895.4 mAh/g. The high reversible specific capacity, perfect cyclability, and rate performance are attributed to the unique urchin-like NiCo₂O₄ microspheres, which can alleviate the volume expansion and shorten the diffusion path of ions and electrons during lithiation/delithiation process. The self-standing urchin-like NiCo₂O₄ microspheres may be a very promising candidate in place of the commercial graphite-based anode materials for high-performance LIBs.     

One-step solid-state synthesis of nanosized LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> cathode material with power properties

A simple one-step solid state reaction way of preparing nanosized LiMn₂O₄ powders with high-rate properties is investigated. Oxalic acid is used as a functional material to lose volatile gases during the process of calcining in order to control the morphology and change the particle size of materials. The results of X-ray diffraction and scanning electron microscopy show that particle size of materials decreases with the increase of the oxalic acid content. The electrochemical test results indicate that optimal LiMn₂O₄ particles (S_0.5) is synthesized when the molar ratios of oxalic acid and total Mn source are 0.5:1. It also manifests that LiMn₂O₄ sample with middle size has the optimal electrochemical performance among five samples instead of the smallest LiMn₂O₄ sample. The obtained sample S_0.5 with middle size exhibits a high initial discharge capacity of 125.8 mAh g^?1 at 0.2C and 91.4% capacity retention over 100 cycles at 0.5C, superior to any one of other samples. In addition, when cycling at the high rate of 10C, the optimal S_0.5 in this work could still reach a discharge capacity of 80.8 mAh g^?1. This observation can be addressed to the fact that the middle size particles balance the contradictory of diffusion length in solid phase and particle agglomeration, which leads to perfect contacts with the conductive additive, considerable apparent Li-ion diffusion rate, and the optimal performance of S_0.5.     

Synthesis and pseudocapacitive investigation of LiCr x Mn2-x O4 cathode material for aqueous hybrid supercapacitor

A series of Cr-substituted LiMn₂O₄ samples (LiCr _x Mn_2-x O₄, 0?≤?x?≤?0.3) were synthesized by a urea-assisted combustion method to enhance pseudocapacitive properties of LiMn₂O₄ material in aqueous electrolyte. Their structure and morphology were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The LiCr _x Mn_2-x O₄ and activated carbon (AC) electrode were used as the cathode and anode in hybrid supercapacitors, respectively, which capacitive properties were determined by cyclic voltammetry (CV), galvanostatic charge/discharge test, and electrochemical impedance spectroscopy (EIS) in Li₂SO₄ solution. The results revealed that the partial substitution of Mn³⁺ by Cr³⁺ decreased initial capacity, but it prevented capacity fading. In the working voltage of 0–1.4 V, the AC/LiCr_0.1Mn_1.9O₄ capacitor delivered an initial specific capacitance of 41.6 F g^?1 (based on the total active mass of two electrodes) at a current density of 100 mA g^?1 in 1 M Li₂SO₄ solution. After 1,000 cycles, its capacity loss was only 1.7 %.     

Layered lithium-rich oxide nanoparticles: low-temperature synthesis in mixed molten salt and excellent performance as cathode of lithium-ion battery

Layered lithium-rich oxide, 0.5Li₂MnO₃·0.5LiMn_1/3Ni_1/3Co_1/3O₂, is synthesized in a mixed molten salt of KCl and LiCl under 750 °C. Its morphology and structure are characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption and desorption isotherm, and its performances as cathode of lithium-ion battery are investigated by charge–discharge test and electrochemical impedance spectroscopy, with a comparison of the samples synthesized via solid-state reaction. It is found that the resulting product consists of uniform nanoparticles, 50 nm in average, which possesses a well crystallite layered structure although its synthesis temperature is low and thus exhibits excellent cyclic stability and rate capability. The resulting product delivers an initial discharge capacity of 268 mAh g^?1 at 0.1 C and has a capacity retention of 82% after 100 cycles at 1 C, compared to the 243 mAh g^?1 and 73% for the sample synthesized by solid-state reaction under 900 °C.     

Electrochemical performance of La2O3-coated layered LiNiO2 cathode materials for rechargeable lithium-ion batteries

Uncoated and La₂O₃-coated LiNiO₂ cathode materials were synthesized by polymeric sol gel process using metal nitrate precursors at 600 °C for 10 h. The structure and electrochemical properties of the surface-coated LiNiO₂ materials were characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammetry, charge/discharge and electrochemical impedance spectroscopy techniques. X-ray powder diffraction and SEM result show that no significant bulk structural differences were observed between the lanthanum oxide coated and pristine LiMn₂O₄. The galvanostatic charge/discharge studies on the uncoated and lanthanum oxide-coated LiNiO₂-positive material at 0.5-C rate in the potential range between 3 and 4.5 V revealed that lanthanum oxide-coated positive electrode material has enhanced charge/discharge capacities; 2.0 wt.% of lanthanum oxide-coated LiNiO₂-positive material has satisfied the structural stability, high reversible capacity and high electrochemical performances.     

Lithium manganese aluminum oxide-based full Li-ion battery using carbon fibers as current collectors

Herein, Li-ion battery using carbon fibers instead of conventional aluminum/copper foils as the current collectors is assembled. To achieve the binder-free environment, LiMn_0.97Al_0.03O₂-based fiber type cathode is prepared directly via a two-step strategy involving electroplating and hydrothermal method by forming active materials on the individual carbon fiber. Cu₆Sn₅-based fiber type anode is prepared directly via electroplating and subsequent heat treatment. The resulting LiMn_0.97Al_0.03O₂|Cu₆Sn₅ Li-ion battery using carbon fiber as the current collector functions at about 3 V, with an initial capacity of 180 mAh g^?1 (based on the cathode). The capacity retention is 90 % after 150 cycles. In particular, the battery using phosphate-modified LiMn_0.97Al_0.03O₂-based fiber type electrode demonstrates a better cycling and high rate performance compared to the unmodified counterpart.     

Electrochemical properties of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> prepared with tartaric acid chelating agent

Lithium manganese oxide (LiMn₂O₄) has been prepared using sol-gel technique under acidic (pH = 5.8) and alkaline (pH = 9) conditions with tartaric acid as chelating agent. X-ray studies show that under acidic condition, an Mn₂O₃ peak was observed indicating the presence of impurities. No impurity was observed for LiMn₂O₄ under alkaline conditions. The particle size is mostly in the range of 124 to 185 nm from HR-TEM. The lithium diffusion coefficient, D _Li+ in LiMn₂O₄ is of the order 10^?9 cm² s^?1. By using density functional theory (DFT) calculations, structural properties have been obtained. The specific discharge capacity of the cells with LiMn₂O₄ prepared under alkaline condition and with LiMn₂O₄ prepared under acidic condition discharged at 0.5 C is in the ranges of 132 to 142 and 128 to 139 mAh g^?1, respectively.     

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.     

Synthesis and characterization of LiMn1-x Fe x PO4/carbon nanotubes composites as cathodes for Li-ion batteries

Carbon nanotubes (CNT) coated with LiMn_1-x Fe _x PO₄ (0.2?≤?x?≤?0.8), as possible cathode materials, was synthesized by using a sol–gel process (Polyol method), after annealing under flowing nitrogen. X-ray diffraction (XRD) patterns of the composites confirmed the formation of the olivine structured LiMn_1-x Fe _x PO₄ phase and no secondary phases were detected. The morphological investigation revealed the formation of agglomerates with particles size ranging between 300 and 700 nm. XRD investigation of composites shows difference of the morphology by doping CNT and carbon black in the composites. Transmission electron microscopy shows the growth of nano-sized particles on CNT (20–70 nm) and the agglomeration of primary particles to form secondary particles. The X-ray photoelectron spectroscopy showed that the Fe and Mn ions are in divalent states in the LiMn_1-x Fe _x PO₄ composites. The cyclic voltamograms showed the oxidation peaks of iron and manganese ions at 3.53–3.63 and 4.05–4.33 V, respectively, while the reduction peaks were found at 3.21–3.42 V (iron reduction) and 3.85–3.93 V (manganese reduction) depending on the iron content in the composition. The LiMn_0.6Fe_0.4PO₄/CNT composite (x?=?0.4) (with 20 %?wt CNT) delivered a specific capacity of 120 mAhg^?1 (at a discharge rate of C/20 and RT).     

Characterization of crystallized LiMn2O4 thin films grown by pulsed laser deposition

LiMn₂O₄ thin films were grown on stainless steel substrates at 625°C and 100?mTorr of oxygen by pulsed laser deposition. The deposited film was highly crystallized with an average crystal size of about 260?nm. The initial discharge capacity of the film was about 53.8?µAh?cm^?2?µm^?1 and the capacity decayed at an average rate of about 0.29% per cycle when the film was cycled between 3.0 and 4.5?V vs. Li/Li⁺, with a current density of 20?µA?cm^?2. It was observed that the grains became smaller and the boundaries of grains became obscure after 100 cycles, indicating that manganese dissolution via loss of MnO may be the main factor leading to the capacity fade in pure thin film LiMn₂O₄ electrodes. The apparent diffusion coefficient of Li ions, obtained from cyclic voltammetry scans, was of the order of 10^?12?cm²?s^?1. High charge-transfer resistance was observed at high potentials. Ex-situ X-ray diffraction (XRD) and Raman spectroscopy were used to investigate the structure changes of LiMn₂O₄ thin film with intercalation/de-intercalation of lithium. XRD results revealed a relatively small lattice change with the removal of lithium in crystallized thin film, compared to that of powder LiMn₂O₄ cathode.