Effect of MgF2 coating on the electrochemical performance of LiMn2O4 cathode materials

Spinel LiMn₂O₄ cathode materials were coated with 1.0, 3.0 and 5.0?wt.% of MgF₂ by precipitation, followed by heat treatment at 400?°C for 5?h in air. The effects of MgF₂ coating on the structural and electrochemical properties of LiMn₂O₄ cathodes were investigated using XRD, SEM, and electrochemical tests. XRD and SEM results show that no significant bulk structural differences are observed between the coated and pristine LiMn₂O₄. The charge–discharge tests show that the discharge capacity of LiMn₂O₄ decreases slightly, but the cyclability of LiMn₂O₄ is clearly improved when the amount of the MgF₂ coated was increased to 3.0?wt.%. The 3.0?wt.% MgF₂-coated LiMn₂O₄ exhibits capacity retention of 80.1 and 76.7 % after 100 cycles at room temperature (25?°C) and elevated temperature (55?°C) at a rate of 1?C, respectively, much higher than those of the bare LiMn₂O₄ (70.1 and 61.6 %). The improvement of electrochemical performance is attributed to the suppression of Mn dissolution into the electrolyte via the MgF₂ coating layer.     

Surface modifications of Li-ion battery electrodes with various ultrathin amphoteric oxide coatings for enhanced cycleability

Ultrathin ZnO, ZrO₂, and Al₂O₃ surface coatings are deposited via atomic layer deposition (ALD) with high conformality and atomic scale thickness control to enhance the electrochemical performance of LiMn₂O₄ for applications in lithium ion batteries. Two types of ALD-modified LiMn₂O₄ electrodes are fabricated: one is ALD-coated LiMn₂O₄ composite electrode and the other is electrode composed of ALD-coated LiMn₂O₄ particles and uncoated carbon/polyvinylidenefluoride network. Cycling performance and cyclic voltammetric patterns reveal that ZnO ALD coating is the most effective protective film for improving the electrochemical performance of LiMn₂O₄ at either 25 or 55 °C, followed by ZrO₂ and Al₂O₃. After 100 electrochemical cycles in 1 C at 55 °C, the electrode consisting of LiMn₂O₄ particles coated with six ZnO ALD layers (as thin as ~1 nm) delivers the highest final capacity, more than twice that of the bare electrode. It is also found that amphoteric oxide coating on LiMn₂O₄ particles can enhance the cycleability of LiMn₂O₄ more effectively than coating on the composite electrode. Furthermore, for ALD coating either on the composite electrode or on LiMn₂O₄ particles, the effect of oxide ALD modification for improving capacity retention and increasing specific capacity of LiMn₂O₄ is more phenomenal at elevated temperature than at room temperature.     

The effect of nanolayer AlF<Subscript>3</Subscript> coating on LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> cycle life in high temperature for lithium secondary batteries

The surface of the spinel LiMn₂O₄ was coated with AlF₃ by a chemical process to improve its electrochemical performance at high temperatures. The morphology and structure of the original and AlF₃-coated LiMn₂O₄ samples were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM). All the samples exhibited a pure cubic spinel structure without any impurities in the XRD patterns. It was found that the surfaces of the original LiMn₂O₄ samples were covered with a nanolayer AlF₃ after the treatment. The charge/discharge of the materials were carried at 220 mA/g in the range of 3.0 and 4.4 V at 55°C. While the original LiMn₂O₄ showed 17.8% capacity loss in 50 cycles at 55°C, the AlF₃-coated LiMn₂O₄ (118.1 mA h/g) showed only 3.4% loss of the initial capacity (122.3 mA h/g) at 55°C. It is obvious that the improvement in cycling performance of the coated-LiMn₂O₄ electrode at 55°C is attributed to the presence of AlF₃ on the surface of LiMn₂O₄. Published in Russian in Elektrokhimiya, 2009, Vol. 45, No. 7, pp. 817–819. The article is published in the original     

Electrochemical performance of LiMn2O4 microcubes prepared by a self-templating route

LiMn₂O₄ microcubes with a size of 10–15 μm have been synthesized by a facile self-templating route starting from cubic MnCO₃. The LiMn₂O₄ microcubes exhibit a hierarchical structure, where the cubes are stacked from parallel plates with a thickness of 200 nm, where each plate is composed of interconnected nanoparticles with a size of around 200 nm. The cubic LiMn₂O₄ shows excellent rate capability and high-rate cycling stability. At 10 C, it can yield a discharge capacity of 108 mAh g^?1. A discharge capacity of 88 mAh g^?1 can be retained after 100 cycles at 10 C. The excellent electrochemical performance makes it a promising cathode for high-power Li-ion batteries.     

Morphology-controllable synthesis of LiMn2O4 particles as cathode materials of lithium batteries

We reported a new method for the preparation of morphology-controllable LiMn₂O₄ particles. In this method, dimension-different MnO₂ nanowires synthesized hydrothermally by adjusting the reaction temperature were used as the precursor. The morphology and structure of the resulting products were characterized with scanning electron microscope and X-ray diffraction, and the performances of the prepared LiMn₂O₄ samples as cathode material of lithium batteries were investigated by cyclic voltammetry and galvanostatic charge/discharge test. The results indicate that the morphology of LiMn₂O₄ transforms from tridimensional particle (TP) to unidimensional rod (UR) through quadrate lamina (QL) with increasing the diameter and length of MnO₂ nanowires. Although the cyclic stabilities of LiMn₂O₄-TP, LiMn₂O₄-QL, and LiMn₂O₄-UR are very close (the 0.1 C capacity after 50 cycles is 101, 93, and 99 mAh g^?1 at 25 °C, and 84, 78, and 82 mAh g^?1 at 50 °C, respectively), LiMn₂O₄-QL delivers much higher rate capacity (about 70 mAh g^?1 at 5 C and 30 mAh g^?1 at 10 C) than LiMn₂O₄-TP and LiMn₂O₄-UR (about 20 mAh g^?1 at 5 C, 3 mAh g^?1 at 10 C, 25 mAh g^?1 at 5 C, and 3 mAh g^?1 at 10 C).     

One-step hydrothermal synthesis of LiMn2O4 cathode materials for rechargeable lithium batteries

LiMn₂O₄ cathode materials with high discharge capacity and good cyclic stability were prepared by a simple one-step hydrothermal treatment of KMnO₄, aniline and LiOH solutions at 120–180 °C for 24 h. The aniline/KMnO₄ molar ratio (R) and hydrothermal temperature exhibited an obvious influence on the component and phase structures of the resulting product. The precursor KMnO₄ was firstly reduced to birnessite when R was less than 0.2:1 at 120–150 °C. Pure-phased LiMn₂O₄ was formed when R was 0.2:1, and the LiMn₂O₄ was further reduced to Mn₃O₄ when R was kept in the range of 0.2–0.3 at 120–150 °C. Moreover, LiMn₂O₄ was fabricated when R was 0.15:1 at 180 °C. Octahedron-like LiMn₂O₄ about 300 nm was prepared at 120 °C, and particle size decreased with an increase in hydrothermal temperature. Especially, LiMn₂O₄ synthesized at 150 °C exhibited the best electrochemical performance with the highest initial discharge capacity of 127.4 mAh g⁻¹ and cycling capacity of 106.1 mAh g⁻¹ after 100 cycles. The high discharge capacity and cycling stability of the as-prepared LiMn₂O₄ cathode for rechargeable lithium batteries were ascribed to the appropriate particle size and larger cell volume.     

Facile synthesis of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> microsheets with porous micro-nanostructure as high-rate cathode materials for Li-ion batteries

Porous LiMn₂O₄ microsheets with micro-nanostructure have been successfully prepared through a simple carbon gel-combustion process with a microporous membrane as hard template. The crystal structure, morphology, chemical composition, and surface analysis of the as-obtained LiMn₂O₄ microsheets are characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscope (XPS). It can be found that the as-prepared LiMn₂O₄ sample presents the two-dimensional (2-D) sheet structure with porous structure comprised with nano-scaled particles. As cathode materials for lithium-ion batteries, the obtained LiMn₂O₄ microsheets show superior rate capacities and cycling performance at various charge/discharge rates. The LiMn₂O₄ microsheets exhibit a higher charge and discharge capacity of 137.0 and 134.7 mAh g^?1 in the first cycle at 0.5 C, and it remains 127.6 mAh g^?1 after 50 cycles, which accounts for 94.7% discharge capacity retention. Even at 10 C rate, the electrode also delivers the discharge capacity of 91.0 mAh g^?1 after 300 cycles (93.5% capacity retention). The superior electrochemical properties of the LiMn₂O₄ microsheets could be attributed to the unique microsheets with porous micro-nanostructure, more active sites of the Li-ions insertion/deinsertion for the higher contact area between the LiMn₂O₄ nano-scaled particles and the electrolyte, and better kinetic properties, suggesting the applications of the sample in high-power lithium-ion batteries.     

Effect of Al2O3 -coating on the electrochemical performances of Li3V2(PO4)3/C cathode material

The effect of Al₂O₃ -coating on Li₃V₂(PO₄)₃/C cathode material for lithium-ion batteries has been investigated. The crystalline structure and morphology of the synthesized powders have been characterized by XRD, SEM, and HRTEM, and their electrochemical performances are evaluated by CV, EIS, and galvanostatic charge/discharge tests. It is found that Al₂O₃ -coating modification stabilizes the structure of the cathode material, decreases the polarization of electrode and suppresses the rise of the surface film resistance. Electrochemical tests indicate that cycling performance and rate capability of Al₂O₃-coated Li₃V₂(PO₄)₃/C are enhanced, especially at high rates. The Al₂O₃-coated material delivers discharge capacity of 123.03 mAh g^?1 at 4 C rate, and the capacity retention of 94.15 % is obtained after 5 cycles. The results indicate that Al₂O₃ -coating should be an effective way to improve the comprehensive properties of the cathode materials for lithium-ion batteries.     

Comparison of different soft chemical routes synthesis of nanocrystalline LiMn2O4 and their influence on its physicochemical properties

A comparative study of nanocrystalline spinel LiMn₂O₄ powders prepared by two different soft chemical routes such as solution and sol-gel methods using lithium and manganese acetates are the precursors under different calcination temperatures. The dependence of the physicochemical properties of the spinel LiMn₂O₄ powder has been extensively investigated by using thermal analysis (TGA/DTA), FTIR, X-ray diffraction studies, SEM, specific surface area (BET) and electrical conductivity measurements. The results show that pure LiMn₂O₄ can be prepared from acetate precursors as starting materials at a low temperature of 600°C from solution route and 500°C from sol-gel method. The charge-discharge characteristics and the cycling behavior of Li/1M LiBF₄-EC/DEC electrolyte / LiMn₂O₄cells revealed that LiMn₂O₄ calcined at higher temperatures showed a high initial capacity, while the LiMn₂O₄calcined at lower temperatures exhibited a good cycling behavior.     

Improvement of electrochemical performance for Li-rich spherical Li1.3[Ni0.35Mn0.65]O2+x modified by Al2O3

The Li-rich Li_1.3[Ni_0.35Mn_0.65]O_2+x microspheres are firstly prepared and subsequently transferred into the Al₂O₃-coated Li-rich Li_1.3[Ni_0.35Mn_0.65]O_2+x microspheres by a simple deposition method. The as-prepared samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge/discharge tests. The results reveal that the Al₂O₃-coated Li-rich Li_1.3[Ni_0.35Mn_0.65]O_2+x sample has a typical α-NaFeO₂ layered structure with the existence of Li₂MnO₃-type integrated component, and the Al₂O₃ layer is uniformly coated on the surface of the spherical Li-rich Li_1.3[Ni_0.35Mn_0.65]O_2+x particles with a thickness of about 4 nm. Importantly, the Al₂O₃-coated Li-rich sample exhibits obviously improved electrochemical performance compared with the pristine one, especially the 2 wt.% Al₂O₃-coated sample shows the best electrochemical properties, which delivers an initial discharge capacity of 228 mAh g^?1 at a rate of 0.1 C in the voltage of 2.0–4.6 V, and the first coulombic efficiency is up to 90 %. Furthermore, the 2 wt.% Al₂O₃-coated sample represents excellent cycling stability with capacity retention of 90.9 % at 0.33 C after 100 cycles, much higher than that of the pristine one (62.2 %). Particularly, herein, the typical inferior rate capability of Li-rich layered cathode is apparently improved, and the 2 wt.% Al₂O₃-coated sample also shows a high rate capability, which can deliver a capacity of 101 mAh g^?1 even at 10 C. Besides, the thin Al₂O₃ layer can reduce the charge transfer resistance and stabilize the surface structure of active material during cycling, which is responsible for the improvement of electrochemical performance of the Li-rich Li_1.3[Ni_0.35Mn_0.65]O_2+x .     

Novel method to enhance the cycling performance of spinel LiMn2O4

In this study, a novel method was presented to improve the cycle performance of the spinel LiMn₂O₄ This method is quite different from the traditional way of coating LiMn₂O₄ particle itself with inorganic and organic compounds. 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 means of vacuum evaporation. The pure electrode and the modified electrode were investigated using a combination of scanning electron microscope (SEM), electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and charge–discharge tests. The enhancement of the capacity retention of modified electrode is significant, maintaining 93.5% of the maximum capacity after 200 cycles at charge–discharge rate of C/2, while pure electrode only 63.7%. It was found that the improvement of cycling performance is greatly ascribed to the good electrical conductivity of aluminum film deposited on the surface of spinel LiMn₂O₄.     

Structure and electrochemical performances of co-substituted LiSm x La0.2-x Mn1.80O4 cathode materials for rechargeable lithium-ion batteries

Spinel LiMn₂O₄ and Sm, La co-substituted LiSm _x La_0.2-x Mn_1.80O₄ (x?=?0.05, 0.10 and 0.15) 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 thermogravimetric/differential thermal analysis, X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, cyclic voltammetry, charge/discharge and electrochemical impedance spectroscopy studies. XRD analysis indicated that all the prepared samples were mainly belong to cubic crystal form with Fd3m space group. LiSm_0.10La_0.10Mn_1.80O₄ exhibits capacity retention of 90 % and 82 % after 100 cycles at room temperature (30 °C) and at elevated temperature (50 °C) at a rate of 0.5-C, respectively, much higher than those of the pristine LiMn₂O₄ (74 % and 60 %). Among all the compositions, LiSm_0.10La_0.10Mn_1.80O₄ cathode has improved the structural stability, high-capacity retention, better elevated temperature performance and excellent electrochemical performances of the rechargeable lithium-ion batteries.     

Synthesis and Electrochemical Performance of Urea Assisted Pristine LiMn2O4 Cathode for Li Ion Batteries

We report the synthesis of electrochemically active LiMn₂O₄ nanoparticles at varied temperature and pH values by sol–gel method using urea as a chelating and combusting agent. The effect of pH and annealing temperature on the structure, morphology and electrochemical performance was evaluated. The results obtained by XRD, SEM, TEM, and FTIR show that LiMn₂O₄ has uniform porous morphology and highly crystalline particles that can be obtained at pH 7.0 and 8.0 and at a relatively lower temperature of 600°C. Cyclic voltammetry measurements showed reversible redox reactions with fast kinetics corresponding to Li ions intercalation/deintercalation at 600°C at neutral pH 7.0. Charge/discharge studies carried out at a current rate of 40 mA g^–1 reveal that LiMn₂O₄ synthesized at 600°C and pH 7.0 has the best structural stability and excellent cycling performance.

     

Enhancing the Electrochemical Performance of the LiMn2O4 Hollow Microsphere Cathode with a LiNi0.5Mn1.5O4 Coated Layer

Spinel cathode materials consisting of LiMn₂O₄@LiNi_0.5Mn_1.5O₄ hollow microspheres have been synthesized by a facile solution‐phase coating and subsequent solid‐phase lithiation route in an atmosphere of air. When used as the cathode of lithium‐ion batteries, the double‐shell LiMn₂O₄@LiNi_0.5Mn_1.5O₄ hollow microspheres thus obtained show a high specific capacity of 120 mA h g^?1 at 1 C rate, and excellent rate capability (90 mAhg^?1 at 10 C) over the range of 3.5–5 V versus Li/Li⁺ with a retention of 95 % over 500 cycles.     

Improvement of electrochemical properties of LiNi1/3Mn1/3Co1/3O2 by coating with La0.4Ca0.6CoO3

In this paper, La_0.4Ca_0.6CoO₃-coated LiNi_1/3Mn_1/3Co_1/3O₂ is successfully prepared by the sol–gel method associated with microwave pyrolysis method. The structure and electrochemical properties of the La_0.4Ca_0.6CoO₃-coated LiNi_1/3Co_1/3Mn_1/3O₂ are investigated by using X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), and charge/discharge tests. XRD analyses show that the La_0.4Ca_0.6CoO₃ coating does not change the structure of LiNi_1/3Co_1/3Mn_1/3O₂. The electrochemical performance studies demonstrate that 2 wt.% La_0.4Ca_0.6CoO₃-coated LiNi_1/3Co_1/3Mn_1/3O₂ powders exhibit the best electrochemical properties, with an initial discharge capacity of 156.9 mAh g^–1 and capacity retention of 98.9 % after 50 cycles when cycled at a current density of 0.2 C between 2.75 and 4.3 V. La_0.4Ca_0.6CoO₃ coating can improve the rate performance because of the enhancement of the surface electronic/ionic transportation by the coating layer. EIS results suggest that the coating La_0.4Ca_0.6CoO₃ plays an important role in suppressing the increase of cell impedance with cycling especially for the increase of charge-transfer resistance.     

Enhanced high temperature cycling performance of LiMn2O4/graphite cells with methylene methanedisulfonate (MMDS) as electrolyte additive and its acting mechanism

The effects of methylene methanedisulfonate(MMDS) on the high-temperature(~50℃) cycle performance of LiMn_2O_4/graphite cells are investigated.By addition of 2 wt%MMDS into a routine electrolyte,the high-temperature cycling performance of LiMn204/graphite cells can be significantly improved.The analysis of differential capacity curves and energy-dispersive X-ray spectrometry(EDX) indicates that MMDS decomposed on both cathode and anode.The three-electrode system of pouch cell is used to reveal the capacity loss mechanism in the cells.It is shown that the capacity fading of cells without MMDS in the electrolytes is due to irreversible lithium consumption during cycling and irreversible damage of LiMn_2O_4 material,while the capacity fading of cell with 2 wt%MMDS in electrolytes mainly originated from irreversible lithium consumption during cycling.     

Preparation and cycle performance at high temperature for Li[Ni0.5Co0.2Mn0.3]O2 coated with LiFePO4

Li[Ni_0.5Co_0.2Mn_0.3]O₂ coated with LiFePO₄ was synthesized by a co-precipitation method. It consisted of the parent Li[Ni_0.5Co_0.2Mn_0.3]O₂ as the core and the LiFePO₄ as the coating material, with an average particle diameter of 500 nm. The LiFePO₄-coated Li[Ni_0.5Co_0.2Mn_0.3]O₂ showed no large initial capacity drop in the first cycle, which generally occurred with cathode materials bearing inactive coating layers such as Al₂O₃, ZnO, and MgO. Furthermore, it presented a remarkably improved cycle retention rate of over 89% until 400 cycles at 50 °C. We suggest that the LiFePO₄ coating technique is a very effective tool to improve the cycle performance of Li[Ni_0.5Co_0.2Mn_0.3]O₂ at high temperatures.     

ZrO2- and Li2ZrO3-stabilized spinel and layered electrodes for lithium batteries

Strategies for countering the solubility of LiMn₂O₄ (spinel) electrodes at 50 °C and for suppressing the reactivity of layered LiMO₂ (M=Co, Ni, Mn, Li) electrodes at high potentials are discussed. Surface treatment of LiMn₂O₄ with colloidal zirconia (ZrO₂) dramatically improves the cycling stability of the spinel electrode at 50 °C in Li/LiMn₂O₄ cells. ZrO₂-coated LiMn_0.5Ni_0.5O₂ electrodes provide a superior capacity and cycling stability to uncoated electrodes when charged to a high potential (4.6 V vs Li⁰). The use of Li₂ZrO₃, which is structurally more compatible with spinel and layered electrodes than ZrO₂ and which can act as a Li⁺-ion conductor, has been evaluated in composite 0.03Li₂ZrO₃ · 0.97LiMn_0.5Ni_0.5O₂ electrodes; glassy Li_xZrO_2 + x/2 (0<x⩽2) products can be produced from colloidal ZrO₂ for surface coatings.     

PVP-Assisted ZrO2 coating on LiMn2O4 spinel cathode nanoparticles prepared by MnO2 nanowire templates

LiMn₂O₄ spinel nanorods prepared from nanowire MnO₂ templates were capped with polyvinyl pyrrolidone (PVP) and coated with ZrC₂O₄ precursors in aqueous solution. Upon annealing at 600 °C in air, an amorphous ZrO₂ nanoscale coating layer was obtained on the spinel nanoparticles with a particle size of <100 nm that formed from the splitting of the original spinel nanorods. The electrochemical cycling results clearly showed that nanoscale ZrO₂ coating significantly improved the rate capability and cycle life at 65 °C in spite of very high surface area of the spinel nanoparticles.     

The effect of Al2O3-coating coverage on the electrochemical properties in LiCoO2 thin films

The electrochemical properties of nanoscale Al₂O₃-coated LiCoO₂ thin films were examined as a function of the coating coverage. Al₂O₃-coated LiCoO₂ films showed enhanced cycle-life performance with increasing degree of coating coverage, which was attributed to the suppression of Co dissolution and F⁻ concentration in the electrolyte. Moreover, an Al₂O₃-coating layer with partial coverage clearly improved the electrochemical properties, even at 60 °C or with a water-contaminated electrolyte. Even though metal-oxide coating on LiCoO₂ has been actively investigated, the mechanisms of nanoscale coating have yet to be clearly identified. In this article, surface analysis suggested that the Al₂O₃-coating layer had transformed to an AlF₃ ∙3H₂O layer during cycling, which inhibited the generation of HF by scavenging H₂O molecules present in the electrolyte.