A study on carbon-coated LiNi1/3Mn1/3Co1/3O2 cathode material for lithium secondary batteries

The surface of LiNi_1/3Mn_1/3Co_1/3O₂ was coated with amorphous carbon to enhance the conductivity of the material. Electrochemical studies were performed by assembling 2032 coin cells with lithium metal as an anode. When carbon was coated on the surface, the LiNi_1/3Mn_1/3Co_1/3O₂ cathode material showed an improved rate capability, thermal stability, and cycle performance.     

Synthesis and electrochemical performance of LiNi0.6Co0.2Mn0.2O2 as a concentration-gradient cathode material for lithium batteries

A well-ordered and spherical LiNi0.6Co0.2Mn0.2O2 cathode material was successfully synthesized from Ni and Mn concentration-gradient precursors via co-precipitation. The crystal structure, morphology and electrochemical properties of LiNi0.6Co0.2Mn0.2O2 were characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, and charge-discharge tests. The material delivered an initial discharge capacity of 174.3 mAh/g at 180 mA/g （1 C rate） between 2.8 and 4.3 V and more than 93.1% of that was retained after 100 cycles. In addition, it also exhibited excellent rate capability, high cut-off voltage and temperature performance.     

Synthesis and surface treatment of LiNi1/3Co1/3Mn1/3O2 cathode materials for Li-ion batteries

In order to shorten process time and possibly reduce synthesis cost of LiNi_1/3Co_1/3Mn_1/3O₂, the cathode material was prepared by solution combustion and microwave synthesis routes with reduced duration of calcination. The products were also surface-modified with Al₂O₃ by a mechano-thermal coating process to enhance cyclability. The structure and morphology of the bare and the surface-modified LiNi_1/3Co_1/3Mn_1/3O₂ samples were characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, energy-dispersive spectroscopy, and differential scanning calorimetry techniques. At a 0.1-C rate and between 4.6 and 2.5 V, the products delivered a first-cycle discharge capacity of as much as 195 mA h/g. Surface modification of LiNi_1/3Co_1/3Mn_1/3O₂ with alumina resulted in improved cyclability.     

Nano-LiCoO2 as cathode material of large capacity and high rate capability for aqueous rechargeable lithium batteries

Crystalline nanoparticles of LiCoO₂ are prepared by a sol–gel method at 550 °C and characterized by X-ray diffraction. Their electrochemical behaviors were characterized by cyclic voltammograms, capacity measurement and cycling performance. Results show that the reversible capacity of the nano-LiCoO₂ can be up to 143 mAh/g at 1000 mA/g and still be 133 mAh/g at 10,000 mA/g (about 70C) in 0.5 mol/l Li₂SO₄ aqueous electrolyte. In addition, their cycling behavior is also very satisfactory, no evident capacity fading during the initial 40 cycles. These data present great promise for the application of aqueous rechargeable lithium batteries.     

Electrochemical intercalation kinetics of lithium ions for spinel LiNi0.5Mn1.5O4 cathode material

The crystal structure and electrochemical intercalation kinetics of spinel LiNi_0.5Mn_1.5O₄ such as the resistance of a solid electrolyte interphase (SEI) film, charge transfer resistance (R _ct), surface layer capacitance, exchange current density (i ₀), and chemical diffusion coefficient are evaluated by Fourier transform infrared (FT-IR) and electrochemical impedance spectroscopy (EIS), respectively. FT-IR shows that LiNi_0.5Mn_1.5O₄ thus obtained has a cubic spinel structure, which can be indexed in a space group of Fd3m with a disordering distribution of Ni. EIS indicates that R _s is almost a constant at different states of charge. The thickness of SEI film increases with increasing of the cell voltage. R _ct values evidently decreases when lithium ions deintercalated from the cathode in the voltage range from OCV to 4.6 V, and R _ct value increases with increasing potential of deintercalation over 4.7 V. i ₀ varies between 0.2 and 1.6 mA cm^?2, and the solid phase diffusion coefficient of Li⁺ changed depending on the electrode potential in the range of 10^?11–10^?9 cm² s^?1.     

LiMn2O4 nanorods as a super-fast cathode material for aqueous rechargeable lithium batteries

LiMn₂O₄ nanorods were prepared by a facile hydrothermal method in combination with traditional solid-state reactions and characterized by X-ray diffraction analysis. Their electrochemical behavior was tested by cyclic voltammetry and repeated charge/discharge cycling. Results show that the reversible intercalation/deintercalation of Li-ions into/from LiMn₂O₄ cathode can yield up to 110 mAh/g at 4.5 C, and still retains 88% at the very large charge rate of 90 C with well-defined charge and discharge plateaus. It presents very high power density, up to 14.5 kW/kg, and very excellent cycling behavior, 94% capacity retention after 1200 cycles. It is thus a competitor for LiFePO₄.     

CoAl2O4包覆LiNi1/3Co1/3Mn1/3O2的电化学性能

通过共沉淀法制得类球形锂离子电池正极材料LiNi_1/3Co_1/3Mn_1/3O₂,并用非水相共沉法对其进行CoAl₂O₄包覆得到LNCMO(x). 采用X射线衍射（XRD）、扫描电子显微术（SEM）和透射电子显微术（TEM）测试材料的结构和观察材料形貌. 结果表明,CoAl₂O₄在材料表面形成8 nm均匀包覆层,未改变主体材料的结构. 电化学性能测试表明,1%（by mass）CoAl₂O₄包覆量的LiNi1/3Co1/3Mn1/3O2材料（LNCMO(1)）高充电电压（3.0 ~ 4.6 V,150 mA·g^-1）100周期循环放电容量保持率为93.7%（无包覆LNCMO(0)保持率为74.4%）;55 °C高温100周期循环容量保持率为77%（无包覆LNCMO(0)保持率17%）. XRD和电感耦合等离子体原子发射光谱（ICP-AES）测试表明,CoAl₂O₄包覆的LNCMO(x)材料可有效地减缓材料中Mn离子在电解液的溶解,提高材料结构稳定性和热稳定性.     

锂离子电池正极材料LiNi_0.5Mn_1.5O_4表面包覆CuO的研究

本文首先通过共沉淀法和固相球磨法制备了纳米级的LiNi0.5Mn1.5O4高电压正极材料,然后通过溶胶-凝胶法制备了表面包覆CuO的CuO-LiNi0.5Mn1.5O4复合材料.通过对CuO包覆量为1%,3%和5%的复合材料的电化学性能对比,发现当包覆量为1%时,材料的性能最佳.在1 C下,材料的放电比容量高达126.1 mA h g?1,循环100次后容量保持率在99.5%.CuO包覆在纳米LiNi0.5Mn1.5O4材料表面,阻止电解液与活性颗粒的直接接触,削弱了电解液与LiNi0.5Mn1.5O4的相互作用,进而在一定程度上减缓了电解液的分解;CuO的包覆同时还缓解了电解液中HF对材料的攻击,阻止了锰的溶解和由此带来的结构改变,进而提高了材料的循环稳定性.     

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%.     

Preparation and characterization of carbon-coated Li[Ni1/3Co1/3Mn1/3]O2 cathode material for lithium-ion batteries

The carbon-coated Li[Ni_1/3Co_1/3Mn_1/3]O₂ was synthesized from the porous Li[Ni_1/3Co_1/3Mn_1/3]O₂ precursor using citric acid as the carbon source. The electrochemical results showed that both cycling performance and rate capability were improved by the carbon-coating of the Li[Ni_1/3Co_1/3Mn_1/3]O₂ materials. It is proposed that the enhanced electrochemical properties by the carbon-coating are attributed to the increased electronic conductivity because the carbon distributed among the surfaces of spherical Li[Ni_1/3Co_1/3Mn_1/3]O₂ powders favored the transference of electron and reduced cell polarization.     

Electrochemical performance of sulfur composite cathode materials for rechargeable lithium batteries

The structure and characteristic of carbon materials have a direct influence on the electrochemical performance of sulfur-carbon composite electrode materials for lithium-sulfur battery.In this paper,sulfur composite has been synthesized by heating a mixture of elemental sulfur and activated carbon,which is characterized as high specific surface area and microporous structure.The composite,contained 70%sulfur,as cathode in a lithium cell based on organic liquid electrolyte was tested at room temperature....     

Electrochemical behavior of Li[Li0.2Co0.3Mn0.5]O2 as cathode material in Li2SO4 aqueous electrolyte

Layered, lithium-rich Li[Li_0.2Co_0.3Mn_0.5]O₂ cathode material is synthesized by reactions under autogenic pressure at elevated temperature (RAPET) method, and its electrochemical behavior is studied in 2?M Li₂SO₄ aqueous solution and compared with that in a non-aqueous electrolyte. In cyclic voltammetry (CV), Li[Li_0.2Co_0.3Mn_0.5]O₂ electrode exhibits a pair of reversible redox peaks corresponding to lithium ion intercalation and deintercalation at the safe potential window without causing the electrolysis of water. CV experiments at various scan rates revealed a linear relationship between the peak current and the square root of scan rate for all peak pairs, indicating that the lithium ion intercalation–deintercalation processes are diffusion controlled. The corresponding diffusion coefficients are found to be in the order of 10^?8?cm²?s^?1. A typical cell employing Li[Li_0.2Co_0.3Mn_0.5]O₂ as cathode and LiTi₂(PO₄)₃ as anode in 2?M Li₂SO₄ solution delivers a discharge capacity of 90?mA?h g^?1. Electrochemical impedance spectral data measured at various discharge potentials are analyzed to determine the kinetic parameters which characterize intercalation–deintercalation of lithium ions in Li[Li_0.2Co_0.3Mn_0.5]O₂ from 2?M Li₂SO₄ aqueous electrolyte.     

ZnO包覆LiNi1/3Co1/3Mn1/3O2的表面结构和电化学性能

在LiNi_1/3Co_1/3Mn_1/3O₂正极材料表面包覆ZnO,通过X射线衍射（XRD）和光电子能谱（XPS）分析包覆层对正极材料表面状态的改变,并考察了改性后材料的放电容量、首次不可逆容量等电化学性能变化. 结果表明：ZnO主要存在于材料表面并影响着材料表面组成和电化学性质,材料表面镍和锰的含量随着包覆量的增加而增大;400 ^oC热处理可使过渡金属与锌在材料表面形成复合氧化物,过渡金属的结合能增大;包覆2%（by mass,下同）的ZnO可有效抑制55 ^oC下充放电时3.6 V附近的不可逆反应,提高了材料的首次库仑效率;包覆2% ZnO的电池材料在55 ^oC/0.5C的放电比容量和循环寿命最佳.     

准固态锂离子电池正极材料柱[5]醌的研究

锂离子电池的有机正极材料由于具有比容量高、环境友好和廉价等优点,近年来成为研究的热点.但是,有机电极材料在液态电解液中的溶解流失易导致其容量迅速衰减,严重限制了它们的实际应用.本工作基于聚(甲基丙烯酸酯)/聚乙二醇的准固态电解质,考察了以柱[5]醌为正极的准固态锂二次电池的电化学性能.结果显示,柱[5]醌正极不仅保持了高容量的特性(首次放电容量410 mA h/g),并且循环寿命得到了有效提高.0.2 C下循环100周后,电极的容量保持率为88.5%,显示了柱[5]醌在高比能量准固态锂离子电池中的应用潜力.     

Mesoporous and nanowire Co3O4 as negative electrodes for rechargeable lithium batteries

The conversion reactions associated with mesoporous and nanowire Co(3)O(4) when used as negative electrodes in rechargeable lithium batteries have been investigated. Initially, Li is intercalated into Co(3)O(4) up to x approximately 1.5 Li in Li(x)Co(3)O(4). Thereafter, both materials form a nanocomposite of Co particles imbedded in Li(2)O, which on subsequent charge forms CoO. The capacities on cycling increase on initial cycles to values exceeding the theoretical value for Co(3)O(4) + 8 Li(+) + 8e(-) --> 4 Li(2)O + 3 Co, 890 mAhg(-1), and this is interpreted as due to charge storage in a polymer layer that forms on the high surface area of nanowire and mesoporous Co(3)O(4). After 15 cycles, the capacity decreases drastically for the nanowires due to formation of grains that are separated one from another by a thick polymer layer, leading to electrical isolation. In contrast, the mesoporous Co(3)O(4) losses its mesoporosity and forms a morphology similar to bulk Co(3)O(4) (Co particles imbedded in Li(2)O matrix) with which it exhibits a similar capacity on cycling. In contrast to mesoporous lithium intercalation compounds, which show superior capacity at high rates compared to bulk materials, mesoporosity does not seem to improve the capacity of conversion reactions on extended cycling. If, however, mesoporosity could be retained during the conversion reaction, then higher capacities could be obtained in such systems.     

锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2的制备及其电化学性能

以Ni1/3Co1/3Mn1/3(OH)2(2)和Li2CO3为原料,在空气气氛中,经过高温热处理工艺制备了高结晶度的锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2(1)。正交试验确定最佳工艺条件为:2 0.3 mol,n(Li):n(2)=1.2,于950℃反应13 h。电化学性能研究结果表明,在2.7 V～4.6 V,电流密度16 mA.g-1时,1的首次放电比容量为203.4 mAh.g-1;经16 mA.g-1循环2次,32 mA.g-1循环9次,80 mA.g-1循环20次后放电比容量为164.1 mAh.g-1。     

LiNi0.8Co0.15Al0.05O2 coated by chromium oxide as a cathode material for lithium-ion batteries

Journal of Solid State Electrochemistry - LiNi0.8Co0.15Al0.05O2 (NCA) material was decorated with different contents of Cr2O3 (0.01–2 wt%) via a precipitation technique followed by...     

Study of lithium ion intercalation/de-intercalation into LiNi1/3Mn1/3Co1/3O2 in aqueous solution using electrochemical impedance spectroscopy

The mechanism of lithium ion intercalation/de-intercalation into LiNi_1/3Mn_1/3Co_1/3O₂ cathode material prepared by reactions under autogenic pressure at elevated temperatures method is investigated both in aqueous and non-aqueous electrolytes using electrochemical impedance spectroscopy (EIS) technique. In accordance with the results obtained an equivalent circuit is used to fit the impedance spectra. The kinetic parameters of intercalation/de-intercalation processes are evaluated with the help of the same equivalent circuit. The dependence of charge transfer resistance (R _ct), exchange current (I ₀), double layer capacitance (C _dl), Warburg resistance (Z _w), and chemical diffusion coefficient (D _Li+) on potential during intercalation/de-intercalation is studied. The behavior of EIS spectra and its potential dependence is studied to get the kinetics of the mechanism of intercalation/de-intercalation processes, which cannot be obtained from the usual electrochemical studies like cyclic voltammetry. The results indicate that intercalation and de-intercalation of lithium ions in aqueous solution follows almost similar mechanism in non-aqueous system. D _Li+ values are in the range of 10^?8 to 10^?14?cm²?s^?1 in aqueous 5?M LiNO₃ and that in non-aqueous 1?M LiAsF₆/EC+DMC electrolyte is in the order of 10^?12?cm²?s^?1 during the intercalation/de-intercalation processes. A typical cell LiTi₂ (PO4)₃/5?M LiNO₃/LiNi_1/3Mn_1/3Co_1/3O₂ is constructed and the cycling stability is compared to that with an organic electrolyte.