Electrochemical cyclability of oxysulfide spinel Li1.03Al0.2Mn1.8O3.96S0.04 material for lithium secondary batteries

Oxysulfide spinel, Li_1.03Al_0.2Mn_1.8O_3.96S_0.04 with well-developed octahedral structure was synthesized by a sol-gel method using glycolic acid as a chelating agent. The structural integrity of the oxysulfide spinel was characterized by charge–discharge cycling experiments and X-ray diffraction (XRD). The Li_1.03Al_0.2Mn_1.8O_3.96S_0.04 electrode shows excellent cyclability. The oxysulfide spinel after cycling retains its original cubic spinel phase in all operating voltage regions (4.4–1.15 V).     

Enhanced electrochemical performance of Li1.2Ni0.2Mn0.6O2 cathode materials through facile layered/spinel phase tuning

Journal of Solid State Electrochemistry - Series Li1.2Ni0.2Mn0.6O2 (LNMO) cathode materials have been synthesized by an improved one-step solvothermal method. Structural characterization reveals...     

Thermal induced changes in crystal structure and electronic states of Li-ion cathode materials based on Li–Mn–O–S system

Sulphur substitution of oxygen in LiMn₂O₄ spinel destroyed the ideal symmetry of MnO₆ octahedrons. In consequence, the phase change at about room temperature is strongly retarded, manifested by lowering heat of the transition and hysteresis of the temperature dependence of electrical conductivity. The optimal conditions for preparation of sulphur substituted spinel LiMn₂O_4–yS_y have been determined.     

Synthesis of high voltage (4.9 V) cycling LiNixCoyMn(1-x-y)O2 cathode materials for lithium rechargeable batteries

Layered mixed oxides LiNi(x)Co(y)Mn(1-x-y)O(2) (0 ≤x, y≤ 0.5) synthesized by a sol-gel method using tartaric acid as a chelating agent, and their structural and electrochemical properties are investigated by thermal analysis, XRD, SEM, FT-IR and XPS studies. The higher composition of Co leads to cation disorder and shrinks the cell volume. Electrochemical behaviour of the synthesized materials is evaluated by Galvanostatic charge/discharge studies using 2016 type coin cells. The cycling studies are carried out in the voltage limits of 2.7 to 4.6, 4.8 and 4.9 V at current rates of C/10 and C/5 respectively. The composition LiNi(0.4)Co(0.1)Mn(0.5)O(2) exhibits an average discharge capacity of 192 mA h g(-1) at the current density of 0.612 mA cm(-2) (C/5) in the voltage range of 2.7-4.9 V as compared to the discharge capacity of 155 and 175 mA h g(-1) in the potential range of 2.7-4.6 and 2.7-4.8 V over the 50 investigated cycles. The effect of higher charge voltage at 4.9 V on the electrochemical performance of LiNi(x)Co(y)Mn(1-x-y)O(2) oxide materials has not previously been reported.     

Effect of crystal morphology of ultrahigh-nickel cathode materials on high temperature electrochemical stability of lithium ion batteries

Higher nickel content endows Ni-rich cathode materials LiNi_xCo_yMn_1-x-yO₂(x>0.6) with higher specific capacity and high energy density, which is regarded as the most promising cathode materials for Li-ion batteries. However, the deterioration of structural stability hinders its practical application, especially under harsh working conditions such as high-temperature cycling. Given these circumstances, it becomes particularly critical to clarify the i...     

Dual-modification of Gd2O3 on the high-voltage electrochemical properties of LiNi0.8Co0.1Mn0.1O2 cathode materials via the solid-state method

Journal of Solid State Electrochemistry - In this paper, the dual-modified LiNi0.8Co0.1Mn0.1O2 via Gd2O3 is successfully obtained by the solid-state method. The phenomenon of Li/Ni cation mixing...     

Significant improved electrochemical performance of Li(Ni1/3Co1/3Mn1/3)O2 cathode on volumetric energy density and cycling stability at high rate

Li(Ni_1/3Co_1/3Mn_1/3)O₂ microspheres with a tap density of 2.41 g cm⁻³ have been synthesized for applications in high power and high energy systems, using a simple rheological phase reaction route. Cyclic voltammograms (CV) showed no shift of anodic and cathodic peaks centred at 3.81, 3.69 V for the Ni²⁺/Ni⁴⁺ couple after first cycle. The results of power pulse area specific impedance (ASI) and differential scanning calorimetry (DSC) tests showed lower power impedance and increased thermal stability of the electrode at high rate. These merits mentioned above provided significant improved capacity and rate performance for Li(Ni_1/3Co_1/3Mn_1/3)O₂ microspheres, which 159, 147 mAh g⁻¹ discharge capacity was delivered after 100 cycles between 2.5–4.6 V vs. Li at a different discharge rate of 2.5 C (500 mA g⁻¹), 5 C and a constant 0.5 C charge rate, respectively.     

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.     

Physicochemical properties of Mn1.45Co1.45Cu0.1O4 spinel coating deposited on the Crofer 22 H ferritic steel and exposed to high-temperature oxidation under thermal cycling conditions

Journal of Thermal Analysis and Calorimetry - The Crofer 22 H ferritic steel substrate was coated with an Mn1.45Co1.45Cu0.1O4 spinel by means of electrophoresis. After high-temperature oxidation...     

Effect of Na2S treatment on the structural and electrochemical properties of Li1.2Mn0.54Ni0.13Co0.13O2 cathode material

Journal of Solid State Electrochemistry - The electrochemical performances of Li1.2Mn0.54Ni0.13Co0.13O2 cathode material are enhanced through hydrothermal approach using Na2S solution as a medium....     

Comprehensive reinvestigation on the initial coulombic efficiency and capacity fading mechanism of LiNi0.5Mn1.5O4 at low rate and elevated temperature

The effect of different membranes and aluminum current collectors on the initial coulombic efficiency of LiNi_0.5Mn_1.5O₄/Li was investigated, and the cycling performance at different rates and temperatures and the storage performance at 60 °C for a week are discussed for LiNi_0.5Mn_1.5O₄/Li. The results show that the lower initial coulombic efficiency is associated with the lower decomposition voltage of the commercial membrane and electrolyte, and the instability of aluminum current collector under the higher voltage. In addition, both versions of LiNi_0.5Mn_1.5O₄ can deliver about 115 mA?h g^?1 of initial discharge capacity at 1 C at 25 °C and 60 °C; however, it retains only 61.57 % of its initial capacity after the 130th cycles at 60 °C, which is much lower than the 94.46 % rate observed for LiNi_0.5Mn_1.5O₄ at 25 °C, and the cycling performance of the material at 1 C is better than that at 0.5 C. Meanwhile, the initial discharge capacity at 0.1 C after storing at 60 °C is 119.3 mA?h g^?1, which is only a little lower than 121.5 mA?h g^?1 recorded before storing; moreover, the spinel structure and surface state of LiNi_0.5Mn_1.5O₄ after storing at 60 °C has not been changed basically. These results indicate that the electrochemical stability of electrolyte is also related to the temperature. The serious capacity fading of LiNi_0.5Mn_1.5O₄ at 60 °C is attributed to the severe oxidation decomposition and the thermal decomposition in the range of cut-off voltage of the materials, and then the decomposition products interact with active materials to form a solid interface phase, leading to the larger electrode polarization and irreversible capacity loss. Meanwhile, the worse cycling performance at 0.5 C than that at 1 C is attributed to the longer interaction time between the electrolyte and the active materials. However, the storage performance of LiNi_0.5Mn_1.5O₄ corresponds to the thermal stability of electrolyte to a certain extent.     

A comparative study of particle size and hollowness of LiNi1/3Co1/3Mn1/3O2 cathode materials for high-power Li-ion batteries: effects on electrochemical performance

Journal of Solid State Electrochemistry - It is well known that reducing particle size and/or hollowing the particles improves the electrochemical performance, especially the rate capability, of...