Improving the high-temperature performance of LiMn2O4 spinel electrodes by coating the active mass with MgO via a sonochemical method

LiMn₂O₄ spinel coated sonochemically with MgO was studied as an active mass in composite cathodes in standard Li electrolyte solutions for Li-ion batteries at 60 °C. Solutions comprising 1 M LiPF₆ in a mixture of ethylene, dimethyl, and diethyl carbonates (EC–DMC–DEC; 2:2:1) were used. It was possible to obtain LiMn₂O₄ particles fully covered by porous magnesia films that allow a free transport of Li-ions. Electrodes comprising LiMn₂O₄, modified by MgO showed a higher capacity retention compared to the electrodes comprising an uncoated active mass, specially at elevated temperatures. We suggest that the presence of an MgO film on the surface of the LiMn₂O₄ particles, reduces the detrimental effect of HF contamination present in LiPF₆ solutions, reduces the electrodes’ impedance and improves their kinetics.     

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.     

Thermal processes in the systems with Li-battery cathode materials and LiPF6 -based organic solutions

Thermodynamic instability of positive electrodes (cathodes) in Li-ion batteries in humid air and battery solutions results in capacity fading and batteries degradation, especially at elevated temperatures. In this work, we studied thermal interactions between cathode materials Li₂MnO₃, xLi₂MnO₃ ^.(1???x)Li(MnNiCo)O₂,LiNi_0.33Mn_0.33Co_0.33O₂, LiNi_0.4Mn_0.4Co_0.2O₂, LiNi_0.8Co_0.15Al_0.05O₂ LiMn_1.5Ni_0.5O₄, LiMn(or Fe)PO₄, and battery solutions containing ethylene carbonate (EC) or propylene carbonate (PC), dimethyl carbonate (DMC) or ethylmethyl carbonate (EMC) and LiPF₆ salt in the temperature range of 40–400 °C. It was found that these materials are stable chemically and well performing in LiPF₆-based solutions up to 60 °C. The thermal decomposition of the electrolyte solutions starts >180 °C. The macro-structural transformations of cathode materials upon exothermic reactions were studied by transmission electron microscopy (TEM), X-ray difraction (XRD) and Raman spectroscopy. Differential scanning calorimetry (DSC) studies have shown that the exothermic reactions in the temperature range of 60–140 °C lead to partial decomposition of both the cathode material and electrolyte solution. The systems thus formed consisted of partially decomposed solutions and partially chemically delithiated cathode materials covered by reactions products. Thermal reactions terminate and this system reaches equilibrium at about 120 °C. It remains stable up to the beginning of the solution decomposition at about 180 °C. The increased content of surface Li₂CO₃ is found to significantly affect the thermal processes at high temperature range due to extensive exothermic decomposition at low temperatures.     

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.     

Rational Screening of High-Voltage Electrolytes and Additives for Use in LiNi0.5Mn1.5O4-Based Li-Ion Batteries

In the present work, we focus onthe experimental screening of selected electrolytes, which have been reported earlier in different works, as a good choice for high-voltage Li-ion batteries. Twenty-four solutions were studied by means of their high-voltage stability in lithium half-cells with idle electrode (C+PVDF) and the LiNi_0.5Mn_1.5O₄-based composite as a positive electrode. Some of the solutions were based on the standard 1 M LiPF₆ in EC:DMC:DEC = 1:1:1 with/without additives, such as fluoroethylene carbonate, lithium bis(oxalate) borate and lithium difluoro(oxalate)borate. More concentrated solutions of LiPF₆ in EC:DMC:DEC = 1:1:1 were also studied. In addition, the solutions of LiBF₄ and LiPF₆ in various solvents, such as sulfolane, adiponitrile and tris(trimethylsilyl) phosphate, atdifferent concentrations were investigated. A complex study, including cyclic voltammetry, galvanostatic cycling, impedance spectroscopy and ex situ PXRD and EDX, was applied for the first time to such a wide range of electrolytesto provide an objective assessment of the stability of the systems under study. We observed a better anodic stability, including a slower capacity fading during the cycling and lower charge transfer resistance, for the concentrated electrolytes and sulfolane-based solutions. Among the studied electrolytes, the concentrated LiPF₆ in EC:DEC:DMC = 1:1:1 performed the best, since it provided both low SEI resistance and stability of the LiNi_0.5Mn_1.5O₄ cathode material.     

Effect of LiPF<Subscript>6</Subscript> on the thermal behaviors of four organic solvents for lithium ion batteries

The thermal behaviors of four organic solvents with/without LiPF₆ were measured by C80 microcalorimeter at a 0.2°C min⁻¹ heating rate. With the addition of 1 M LiPF₆, the ethylene carbonate (EC) and propylene carbonate (PC) show the exothermic peaks at elevated temperature, which lessen their stabilities. The exothermic peak temperatures of EC and PC based LiPF₆ solutions are at 212 and 223°C, respectively, in argon filled vessel. However, two endothermic peak temperatures were detected in diethyl carbonate (DEC) based LiPF₆ solution at 182 and 252.5°C, respectively, in argon filled vessel. Dimethyl carbonate (DMC) based LiPF₆ solution shows two endothermic peak temperatures at 68.5 and 187°C in argon filled vessel at elevated temperature. Consequently, it is concluded that LiPF₆ play a key role in the thermal behavior of its organic solution.     

Synthesis and characterization of submicron size particles of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> by microemulsion route

Among the various positive electrode materials investigated for Li-ion batteries, spinel LiMn₂O₄ is one of the most important materials. Small particles of the active materials facilitate high-rate capability due to large surface to mass ratio and small diffusion path length. The present work involves the synthesis of submicron size particles of LiMn₂O₄ in a quaternary microemulsion medium. The precursor obtained from the reaction is heated at different temperatures in the range from 400 to 900 °C. The samples heated at 800 and 900 °C are found to possess pure spinel phase with particle size <200 nm, as evidenced from XRD, SEM, and TEM studies. The electrochemical characterization studies provide discharge capacity values of about 100 mAh g⁻¹ at C/5 rate, and there is a moderate decrease in capacity by increasing the rate of charge–discharge cycling. Studies also include charge–discharge cycling and ac impedance studies in temperature range from −10 to 40 °C. Impedance data are analyzed with the help of an equivalent circuit and a nonlinear least squares fitting program. From temperature dependence of charge-transfer resistance, a value of 0.62 eV is obtained for the activation energy of Mn³⁺/Mn⁴⁺ redox process, which accompanies the intercalation/deintercalation of the Li⁺ ion in LiMn₂O₄.     

尖晶石LiMn2O4高温电化学容量衰减及改进

综述了高温下尖晶石LiMn2O4容量衰减的原因、机理研究和改进它的高温性能的方法以及目前的进展,且指出了可能的提高它的高温性能的途径。     

A novel Et<Subscript>4</Subscript>NBF<Subscript>4</Subscript> and LiPF<Subscript>6</Subscript> blend salts electrolyte for supercapacitor battery

Electrolytes of 1 M blend salts (LiPF₆ and tetraethylammonium tetrafluoroborate, Et₄NBF₄) have been investigated in supercapacitor battery system with composite LiMn₂O₄ and activated carbon (AC) cathode, and Li₄Ti₅O₁₂ anode. The results obtained with the blend salts electrolytes are compared with those obtained with cells build using standard 1 M LiPF₆ dissolved in ethylene carbonate + dimethyl carbonate + ethyl (methyl) carbonate (EC + DMC + EMC, 1:1:1 wt.%) as electrolyte. It is found that the blend salts electrolyte performs better on both electrochemical and galvanostatic cycling stability, especially cycled at 4 C rate. When the concentration of LiPF₆ is 0.2 M and Et₄NBF₄ is 0.8 M, the capacity retention of the battery is 96.23% at 4 C rate after 5,000 cycles, much higher than that of the battery with standard 1 M LiPF₆ electrolyte, which is only 62.35%. These results demonstrate that the blend salts electrolyte can improve the galvanostatic cycling stability of the supercapacity battery. Electrolyte of 0.2 M LiPF₆ + 0.8 M Et₄NBF₄ in EC + DMC + EMC (1:1:1 wt.%) is a promising electrolyte for (LiMn₂O₄ + AC)/Li₄Ti₅O₁₂.     

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.     

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     

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).     

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.     

Ge4+、Sn4+掺杂尖晶石LiMn2O4的合成与电化学表征

使用Ge⁴⁺、Sn⁴⁺作为掺杂离子, 通过高温固相法制备四价阳离子掺杂改性的尖晶石LiMn₂O₄材料. X射线衍射(XRD)和扫描电子显微镜(SEM)分析表明, Ge⁴⁺离子取代尖晶石中Mn⁴⁺离子形成了LiMn_2-xGe_xO₄ (x=0.02,0.04, 0.06)固溶体; 而Sn⁴⁺离子则以SnO₂的形式存在于尖晶石LiMn₂O₄的颗粒表面. Ge⁴⁺离子掺入到尖晶石LiMn₂O₄材料中, 抑制了锂离子在尖晶石中的有序化排列, 提高了尖晶石LiMn₂O₄的结构稳定性; 而在尖晶石颗粒表面的SnO₂可以减少电解液中酸的含量, 抑制酸对LiMn₂O₄活性材料的侵蚀. 恒电流充放电测试表明, 两种离子改性后材料的容量保持率均有较大幅度的提升, 有利于促进尖晶石型LiMn₂O₄锂离子电池正极材料的商业化生产.     

The effect of Al substitution on the reactivity of delithiated LiNi1/3Mn1/3Co(1/3−z)AlzO2 with non-aqueous electrolyte

The high temperature reactions between 1 M LiPF₆ EC:DEC and Al-doped LiNi_1/3Mn_1/3Co_(1/3−z)Al_zO₂ charged to 4.3 V were studied by accelerating rate calorimetry (ARC) and compared with those of charged LiNi_1/3Mn_1/3Co_1/3O₂ and LiMn₂O₄. Al substitution for Co in LiNi_1/3Mn_1/3Co_1/3O₂ improves the thermal stability. Materials with z > 0.06 are less reactive with electrolyte than spinel LiMn₂O₄ at all temperatures studied. The maximum self-heating rate (SHR) attained and the specific capacity decrease as the Al content increases. There is a range of compositions near z = 0.1 that show excellent promise as materials which are both safer than and more energy dense than spinel LiMn₂O₄.     

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.     

Synthesis and electrochemical properties of dual doped spinels LiNi_xAl_yMn_(2-x-y)O_4 via facile novel chelated sol–gel method as possible cathode material for lithium rechargeable batteries

LiMn_2O_4 and LiNi_xAlyMn_(2-x-y)O_4(x= 0.50;y = 0.05-0.50) powders have been synthesized via facile solgel method using Behenic acid as active cheiating agent.The synthesized samples are subjected to physical characterizations such as thermo gravimetric analysis(TG/DTA),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR),field-emission scanning electron microscopy(FESEM),transmission electron microscopy(TEM) and electrochemical studies viz.,galvanostatic cycling properties,electrochemical impedance spectroscopy(EIS) and differential capacity curves(dQ/dE).Finger print XRD patterns of LiMn_2O_4 and LiNi_xAl_yMn_(2-x-y)O_4 fortify the high degree of crystallinity with better phase purity.FESEM images of the undoped pristine spinel illustrate uniform spherical grains surface morphology with an average particle size of 0.5 μm while Ni doped particles depict the spherical grains growth(50nm) with ice-cube surface morphology.TEM images of the spinel LiMn_2O_4 shows the uniform spherical morphology with particle size of(100 nm) while low level of Al-doping spinel(LiNio.5Alo.05Mn1.45O4) displaying cloudy particles with agglomerated particles of(50nm).The LiMn_2O_4 samples calcined at 850℃ deliver the discharge capacity of 130 mAh/g in the first cycle corresponds to 94%coiumbic efficiency with capacity fade of 1.5 mAh/g/cycle over the investigated 10 cycles.Among all four dopant compositions investigated,LiNi_(0.5)Al_(0.05)Mn_(1.45)O_4 delivers the maximum discharge capacity of 126 mAh/g during the first cycle and shows the stable cycling performance with low capacity fade of 1 mAh/g/cycle(capacity retention of 92%) over the investigated 10 cycles.Electrochemical impedance studies of spinel LiMn_2O_4 and LiNi_(0.5)Al_(0.05)Mn_(1.45)O_4 depict the high and low real polarization of 1562 and 1100 Ω.     

Improvement in stability of LiMn2O4 thin-film electrodes by oxygen-plasma irradiation to precursor gel

LiMn₂O₄ thin-film electrodes were prepared by the sol?Cgel method combined with oxygen-plasma irradiation. Oxygen plasma with a power of 10 or 90?W was irradiated to the precursor thin film prepared from lithium acetate, manganese acetate tetrahydrate and polyvinylpyrrolidone on a Pt plate, and then it was fired at 723 or 973?K. X-ray diffraction and Raman measurements indicated that oxygen-plasma irradiation was effective to increase the crystallinity of the resulting LiMn₂O₄. Atomic force microscope observation showed that the particle size of LiMn₂O₄ in the resulting thin-film electrode was decreased and homogeneous distribution of LiMn₂O₄ particles was achieved. Oxidation of the electrolyte at higher potentials was suppressed and capacity retention at 328?K was dramatically improved for the LiMn₂O₄ thin-film electrode obtained at 973?K. The improved electrochemical stability is ascribed to the elimination of organic materials from precursor by oxygen-plasma irradiation.     

Preparation of spherical spinel LiMn2O4 cathode material for lithium ion batteries

A novel process is proposed for synthesis of spinel LiMn₂O₄ with spherical particles from the inexpensive materials MnSO₄, NH₄HCO₃, and NH₃H₂O. The successful preparation started with carefully controlled crystallization of MnCO₃, leading to particles of spherical shape and high tap density. Thermal decomposition of MnCO₃ was investigated by both DTA and TG analysis and XRD analysis of products. A precursor of product, spherical Mn₂O₃, was then obtained by heating MnCO₃. A mixture of Mn₂O₃ and Li₂CO₃ was then sintered to produce LiMn₂O₄ with retention of spherical particle shape. It was found that if lithium was in stoichiometric excess of 5% in the calcination of spinel LiMn₂O₄, the product had the largest initial specific capacity. In this way spherical particles of spinel LiMn₂O₄ were of excellent fluidity and dispersivity, and had a tap density as high as 1.9 g cm^–3 and an initial discharge capacity reaching 125 mAh g^–1. When surface-doped with cobalt in a 0.01 Co/Mn mole ratio, although the initial discharge capacity decreased to 118 mAh g^–1, the 100th cycle capacity retention reached 92.4% at 25°C. Even at 55°C the initial discharge capacity reached 113 mAh g^–1 and the 50th cycle capacity retention was in excess of 83.8%.     

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.