The effects of sulfur doping on the performance of O3-Li0.7[Li1/12Ni1/12Mn5/6]O2 powder

Li_0.7[Li_1/12Ni_1/12Mn_5/6]O₂ and Li_0.7[Li_1/12Ni_1/12Mn_5/6]O_2-yS_y (y=0.1, 0.2, 0.3) powders were synthesized by using a sol-gel method. As-prepared samples showed typical rhombohedral O3 layered structure. The shape of the initial discharge curve for the samples was almost equal to that of the layered structure. However, the electrode materials were transferred from layered to spinel structures with cycling. At the first cycle, Li_0.7[Li_1/12Ni_1/122Mn₂5/6]O₂ and Li_0.7[Li_1/12Ni_1/12 Mn_5/6]O_1.9S_0.1, Li_0.7[Li_1/12Ni_1/12Mn_5/6]O_1.8S_0.2, and Li_0.7[Li_1/12Ni_1/12Mn_5/6]O_1.7S_0.3 delivered the discharge capacities of 238, 230,224, and 226 mAh/g, respectively, with their capacity fading rates of 0.34, 0.21, 0.12, 0.25%/cycle, respectively. The partial substitutions of Ni and S for Mn and O in Li_0.7[Li_1/12Ni_1/12Mn_1/12]O₂ significantly enhanced the electrochemical properties of the lithium manganese oxide materials.     

The effects of Ni and Li doping on the performance of lithium manganese oxide material for lithium secondary batteries

Layered Li_0.7[M_1/6Mn_5/6]O₂ (M=Li, Ni) was synthesized using a sol-gel method. P2-Na_0.7[M_1/6Mn_5/6]O₂ precursor was first synthesized by a sol-gel method, and then O2-Li_0.7[M_1/6Mn_5/6]O₂ was prepared by an ion exchange of Li for Na in P2-Na_0.7[M_1/6Mn_5/6]O₂ precursor. From charge/discharge curves, it was seen that Li_0.7[Li_1/6Mn_5/6]O₂ has two plateaus similar to those observed from a spinel structure, but Li_0.7[Ni_1/6Mn_5/6]O₂ holds a single plateau as observed from a typical layered structure. It was considered that Li_0.7[Li_1/6Mn_5/6]O₂ undergoes a phase transformation from layered to spinel structure during the charge/discharge cycle, but Li_0.7[Ni_1/6Mn_5/6]O₂ maintains O2-layered structure after the cycles. Li_0.7[Ni_1/6Mn_5/6]O₂ was higher in discharge capacity and retention rate than Li_0.7[Li_1/6Mn_5/6]O₂.     

Structural and electrochemical characteristics of Li0.7[Li1/6Mn5/6]O2 synthesized using sol-gel method

Layered O₂-lithium manganese oxide (O₂-Li_0.7[Li_1/6Mn_5/6]O₂) was prepared by ion-exchange of P2-sodium manganese oxide (P2-Na_0.7[Li_1/6Mn_5/6]O₂)· P2-Na_0.7[Li_1/6Mn_5/6]O₂ precursor was first synthesized by using a sol-gel method, and then O₂-Li_0.7[Li_1/6Mn_5/6]O₂ was produced by an ion exchange of Li for Na in the P2-Na_0.7[Li_1/6Mn_5/6]O₂ precursor. Structural and electrochemical analyses suggested that good quality O2-Li_0.7[Li_1/6Mn_5/6]O₂ was prepared from P2-Na_0.7[Li_1/6Mn_5/6]O₂ synthesized at 800 °C for 10 h using glycolic acid as a chelating agent. During the cycle, the discharge profile of the synthesized samples showed two plateaus at around 4 and 3 V, respectively, with a steep slope between the two plateaus. The discharge curve at 3 V escalated with an increase in the cycle number, presenting a phase transition from a layered to a spinel like structure. The sample prepared at 800 ‡C for 10 h using glycolic acid delivered a discharge capacity of 187 mAh/g with small capacity fading.     

High-rate, high capacity ZrO2 coated Li[Li1/6Mn1/2Co1/6Ni1/6]O2 for lithium secondary batteries

Recently, there have been many reports on efforts to improve the rate capability and discharge capacity of lithium secondary batteries in order to facilitate their use for hybrid electric vehicles and electric power tools. In the present work, we present a ZrO₂-coated Li[Li_1/6Mn_1/2Co_1/6Ni_1/6]O₂. The bare Li[Li_1/6Mn_1/2Co_1/6Ni_1/6]O₂ shows a high initial discharge capacity of 224 mAh g⁻¹ at a 0.2 C rate. Owing to the stability of ZrO₂, it was possible to enhance the rate capability and cyclability. After 1 wt% ZrO₂ coating, the ZrO₂-coated Li[Li_1/6Mn_1/2Co_1/6Ni_1/6]O₂ showed a high discharge capacity of 115 mAh g⁻¹ after 50 cycles under a 6 C rate, whereas the bare Li[Li_1/6Mn_1/2Co_1/6Ni_1/6]O₂ showed a discharge capacity of only 40 mAh g⁻¹ and very poor cyclability under the same conditions. Based on results of XRD and EIS measurements, it was found that the ZrO₂ suppressed impedance growth at the interface between the electrodes and electrolyte and prevented collapse of the layered hexagonal structure.     

Particle size effect of Li[Ni0.5Mn0.5]O2 prepared by co-precipitation

Spherical (Ni_0.5Mn_0.5)(OH)₂ with different secondary particle size (3 μm, 10 μm in diameter) was synthesized by co-precipitation method. Mixture of the prepared hydroxide and lithium hydroxide was calcined at 950 °C for 20 h in air. X-ray diffraction patterns revealed that the prepared material had a typical layered structure with space group. Spherical morphologies with mono-dispersed powders were observed by scanning electron microscopy. It was found that the layered Li[Ni_0.5Mn_0.5]O₂ delivered an initial discharge capacity of 148 mAh g⁻¹ (3.0-4.3 V) though the particle sizes were different. Li[Ni_0.5Mn_0.5]O₂ having smaller particle size (3 μm) showed improved area specific impedance due to the reduced Li⁺ diffusion path, compared with that of Li[Ni_0.5Mn_0.5]O₂ possessing larger particle size (10 μm). Although the Li[Ni_0.5Mn_0.5]O₂ (3 μm) was electrochemically delithiated to Li_0.39[Ni_0.5Mn_0.5]O₂, the resulting exothermic onset temperature was around 295 °C, of which the value is significantly higher than that of highly delithiated Li_1−δCoO₂ (∼180 °C).     

Synthesis and electrochemical properties of Li[Li0.07Ni0.1Co0.6Mn0.23]O2 as a possible cathode material for lithium-ion batteries

The layered Li[Li_0.07Ni_0.1Co_0.6Mn_0.23]O₂ materials were synthesized by sol-gel method with glycine or citric acid as chelating agent. The prepared materials were characterized by means of XRD, SEM and Raman spectroscopy. Li/Li[Li_0.07Ni_0.1Co_0.6Mn_0.23]O₂ cells were assembled and subjected to charge-discharge studies at different C rates, viz 0.2, 1, 2 and 4 C. Although the samples showed less discharge capacity at 4 C rate the fade in capacity per cycle is lesser than that of capacity fade at 0.2 C rate. The citric acid assisted sample is found to be superior in terms of discharge capacity, capacity retention rate and also in thermal stability to that of sample prepared with glycine as chelating agent.     

A novel layered Li [Li0.12NizMg0.32−zMn0.56]O2 cathode material for lithium-ion batteries

Layered Li[Li_0.12Ni_zMg_0.32−zMn_0.56]O₂ oxide cathodes containing lithium atoms in the transition metal layers were synthesized and characterized using X-ray diffraction (XRD), galvanostatic cycling, and differential scanning calorimetry (DSC). The Li[Li_0.12Ni_zMg_0.32−zMn_0.56]O₂ cathodes deliver a specific discharge capacity of about 190 mAh/g at room temperature and 236 mAh/g at 55 °C when cycled between 2.7 and 4.6 V versus Li/Li⁺. Excellent capacity retention and smooth potential profiles at room and elevated temperatures over extended cycles suggest that this material does not convert into a spinel structure.     

Electrochemical properties and structural characterization of layered Li[Ni0.5Mn0.5]O2 cathode materials

Layered Li[Ni_0.5Mn_0.5]O₂ materials with high homogeneity and crystallinity were prepared using high speed ball milling. The Li[Ni_0.5Mn_0.5]O₂ electrode delivered a high discharge capacity of 152 mA h g⁻¹ between 2.8 and 4.3 V with excellent cycleability. The TEM analysis showed that the Li[Ni_0.5Mn_0.5]O₂ electrode went through a considerable morphological change without altering its initial layered structure while the electrode retained its initial discharge capacity even after 50 cycles.     

Synthesis and structural characterization of layered Li[Ni1/3Co1/3Mn1/3]O2 cathode materials by ultrasonic spray pyrolysis method

The layered Li[Ni_1/3Co_1/3Mn_1/3]O₂ materials were synthesized by a spray pyrolysis method using citric acid as a polymeric agent. The Li[Ni_1/3Co_1/3Mn_1/3]O₂ powders were characterized by means of X-ray diffraction (XRD), charge/discharge cycling, cyclic voltammetry, and high-resolution transmission electron microscopy (TEM). The discharge capacity increases linearly with the increase of the upper cut-off voltage limit. TEM analysis showed that particles in the as-prepared powder possessed a polycrystalline structure. During cycling, the particle structure is mostly preserved although some surface grains on the polycrystalline particle became separated and transformed to the spinel phase.     

Effect of synthesis condition on the structural and electrochemical properties of Li[Ni1/3Mn1/3Co1/3]O2 prepared by the metal acetates decomposition method

In order to get homogeneous layered oxide Li[Ni_1/3Mn_1/3Co_1/3]O₂ as a lithium insertion positive electrode material, we applied the metal acetates decomposition method. The oxide compounds were calcined at various temperatures, which results in greater difference in morphological (shape, particle size and specific surface area) and the electrochemical (first charge profile, reversible capacity and rate capability) differences. The Li[Ni_1/3Mn_1/3Co_1/3]O₂ powders were characterized by means of X-ray diffraction (XRD), charge/discharge cycling, cyclic voltammetry and SEM. XRD experiment revealed that the layered Li[Ni_1/3Mn_1/3Co_1/3]O₂ material can be best synthesized at temperature of 800 °C. In that synthesized temperature, the sample showed high discharge capacity of 190 mAh g⁻¹ as well as stable cycling performance at a current density of 0.2 mA cm⁻² in the voltage range 2.3-4.6 V. The reversible capacity after 100 cycles is more than 190 mAh g⁻¹ at room temperature.     

Electrochemical and thermal studies of Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 (x = 1/12, 1/4, 5/12, and 1/2)

Samples of the layered cathode materials, Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ (x = 1/12, 1/4, 5/12, and 1/2), were synthesized at 900 °C. Electrodes of these samples were charged in Li-ion coin cells to remove lithium. The charged electrode materials were rinsed to remove the electrolyte salt and then added, along with EC/DEC solvent or 1 M LiPF₆ EC/DEC, to stainless steel accelerating rate calorimetry (ARC) sample holders that were then welded closed. The reactivity of the samples with electrolyte was probed at two states of charge. First, for samples charged to near 4.45 V and second, for samples charged to 4.8 V, corresponding to removal of all mobile lithium from the samples and also concomitant release of oxygen in a plateau near 4.5 V. Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ samples with x = 1/4, 5/12 and 1/2 charged to 4.45 V do not react appreciably till 190 °C in EC/DEC. Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ samples charged to 4.8 V versus Li, across the oxygen release plateau, start to significantly react with EC/DEC at about 130 °C. However, their high reactivity is similar to that of Li_0.5CoO₂ (4.2 V) with 1 μm particle size. Therefore, Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ samples showing specific capacity of up to 225 mAh/g may be acceptable for replacing LiCoO₂ (145 mAh/g to 4.2 V) from a safety point of view, if their particle size is increased.     

Electrochemical performance of Li[Co0.1Ni0.15Li0.2Mn0.55]O2 modified by carbons as cathode materials

To enhance specific capacity, cycle performance and rate-capability of lithium-ion battery cathode materials, the Li[Co_0.1Ni_0.15Li_0.2Mn_0.55]O₂ (LCMNO) is modified by coating them with amorphous carbons and by preparing nanocomposites with nanostructured carbons (carbon nanotube and graphene). The carbon-treated LCMNO powders and their cathodes are characterized by morphological observation, crystalline property analysis, galvanostatic charge–discharge, and electrochemical impedance spectroscopy. The LCMNO nanocomposite shows a superior discharge capacity of ca. 290 mAh g⁻¹ at low C-rates, due to a greater number of active sites embedded by nanostructured carbon species. In contrast, the carbon-coated LCMNO shows higher discharge capacity in high rate regions due to the carbon-coated layer in the carbon-coated LCMNO, suppressing the side reactions and enhancing the electrical conductivity.     

Electrochemical properties of layered Li[Ni1/2Mn1/2]O2 cathode material synthesised by ultrasonic spray pyrolysis

Layered Li[Ni_1/2Mn_1/2]O₂ was synthesized by an ultrasonic spray pyrolysis method. The Li[Ni_1/2Mn_1/2]O₂ powder was characterized by means of X-ray diffraction, charge/discharge test, and cyclic voltammetry. The discharge capacity increases linearly with increase of the upper cut-off voltage limit and attains a high discharge capacity of 187 mA h g^–1 between 2.8 and 4.6 V with excellent cyclability. A cyclic voltammetric study of the Li[Ni_1/2Mn_1/2]O₂ electrode showed only one redox peak implying no structural phase change during cycling.     

Synthesis and characterization of integrated layered nanocomposites for lithium ion batteries

The series of Li[Ni _x M _x Li_1/3-x Mn_2/3-x ]O₂ cathodes, where M is cobalt or chromium with a wide compositional range x from 0 to 0.33, were prepared by hydroxide coprecipitation method with subsequent quenching. The sample structures were investigated using X-ray diffraction results which were indexed completely on the basis of a trigonal structure of space group with monoclinic C2/m phase as expected. The morphologies and electrochemical properties of the samples obtained were compared as the value of x and substituted transition metal. The particle sizes of cobalt-substituted Li[Ni _x Co _x Li_1/3-x Mn_2/3-x ]O₂ samples are much smaller than those of the Li[Ni _x Cr _x Li_1/3-x Mn_2/3-x ]O₂ system. The electrode containing Li[Ni _x Co _x Li_1/3-x Mn_2/3-x ]O₂ with x = 0.10 delivered a discharge capacity of above 200 mAh/g after 10 cycles due to the activation of Li₂MnO₃.     

Stabilizing the structure and suppressing the voltage decay of Li[Li0.2Mn0.54Co0.13Ni0.13]O2 cathode materials for Li-ion batteries via multifunctional Pr oxide surface modification

The development of Li-rich layer cathode materials has been limited by poor cycle, rate performance, phase transformation and voltage decay. To improve these properties, a facile and low-cost wet method is employed to fabricate Pr₆O₁₁ coating layer on Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ nanoparticles. The 3–6 nm Pr₆O₁₁ coating layer is observed on the surface of Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ by HRTEM. Interestingly, HAADF-STEM and EDS analyses show that the transition metal ions and the praseodymium ions mutually infiltrate in the Pr₆O₁₁ coating layer and Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ nanoparticles during calcination. A combination of HAADF-STEM with EDS and XPS studies reveals that Pr₆O₁₁ coating layer is bridged to Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ nanoparticles by the chemical bonds of transition phase Li_1.2M_XPr_1−xO₂. XRD patterns show that all samples are indexed to the layered structure α-NaFeO₂, but the lattice parameters are influenced lightly after Pr₆O₁₁ coating. HRTEM and SAED analyses elucidate that the super large Pr ions surface-doping and the Pr₆O₁₁ coating are verified to suppress the transformation of layer to spinel structure in the bulk nanoparticles after cycles. The sample coated with 3 wt% Pr₆O₁₁ exhibits wonderful electrochemical performance with the first coulomb efficiency of 85.6%, the capacity retention ratio of 97.9% after 50 cycles and the discharge capacity of 162.2 mAh g⁻¹ at 5 C. The resistant of charge transfer and the electrodes polarization are reduced by Pr₆O₁₁ coating according to EIS. Therefore, Pr₆O₁₁, which contains the super large Pr ions, plays two roles: the first one, it is coated on the Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ nanoparticles to optimize the environment of the interface reaction between electrodes and electrolyte; the other one, its Pr ions surface-doping stabilizes the structure in the superficial region of Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ nanoparticles and suppresses the voltage decay. The multifunctional Pr₆O₁₁ can play a significant role in accelerating development of new materials with excellent stabilization and high capacity.     

Insignificant impact of designed oxygen release from high capacity Li[(Ni1/2Mn1/2)xCoy(Li1/3Mn2/3)1/3]O2 (x + y = 2/3) positive electrodes during the cycling of Li-ion cells

The properties of graphite/Li[(Ni_0.5Mn_0.5)_xCo_y(Li_1/3Mn_2/3)_1/3]O₂ (x + y = 2/3, y = 1/12 and 1/6) Li-ion cells are reported. There is an extended plateau near 4.5 V during the first charging of the cells that corresponds to the simultaneous removal of Li and oxygen from the Li[(Ni_0.5Mn_0.5)_xCo_y(Li_1/3Mn_2/3)_1/3]O₂ (x + y = 2/3, y = 1/12 and 1/6) electrodes. The release of this oxygen directly within a Li-ion cell has been a cause for concern. However, it was found that subsequent to O₂ release, Li-ion cells delivered a high reversible positive electrode specific capacity near 250 mAh/g at C/30 between 2.5 and 4.8 V, the cells did not display increased irreversible capacity relative to counterparts having Li metal negative electrodes and the cells retained 85% of their initial capacity after 70 cycles at C/6 between 2.5 and 4.6 V. Therefore, the O₂ released during the first charge does not significantly impact the electrochemical properties of graphite/Li[(Ni_0.5Mn_0.5)_xCo_y(Li_1/3Mn_2/3)_1/3]O₂ (x + y = 2/3) lithium-ion cells.     

High-voltage performance of concentration-gradient Li[Ni0.67Co0.15Mn0.18]O2 cathode material for lithium-ion batteries

A novel Li[Ni_0.67Co_0.15Mn_0.18]O₂ cathode material encapsulated completely within a concentration-gradient shell was successfully synthesized via co-precipitation. The Li[Ni_0.67Co_0.15Mn_0.18]O₂ has a core of Li[Ni_0.8Co_0.15Mn_0.05]O₂ that is rich in Ni, a concentration-gradient shell having decreasing Ni concentration and increasing Mn concentration toward the particle surface, and a stable outer-layer of Li[Ni_0.57Co_0.15Mn_0.28]O₂. The electrochemical and thermal properties of the material were investigated and compared to those of the core Li[Ni_0.8Co_0.15Mn_0.05]O₂ material alone. The discharge capacity of the concentration-gradient Li[Ni_0.67Co_0.15Mn_0.18]O₂ electrode increased with increasing upper cutoff voltage to 4.5 V, and cells with this cathode material delivered a very high capacity, 213 mAh/g, with excellent cycling stability even at 55 °C. The enhanced thermal and lithium intercalation stability of the Li[Ni_0.67Co_0.15Mn_0.18]O₂ was attributed to the gradual increase in tetravalent Mn concentration and decrease in Ni concentration in the concentration-gradient shell layer.     

On the LiCo2/3Ni1/6Mn1/6O2 positive electrode material

LiCo_2/3Ni_1/6Mn_1/6O₂ layered oxide was synthesized by the combustion method that led to a crystalline phase with good homogeneity and low particles size. The structural properties of the prepared positive electrode material were investigated by performing XRD Rietveld refinement. Practically no Li/Ni mixing was detected evidencing that the studied compound adopts almost an ideal α-NaFeO₂ type structure. The Li||LiCo_2/3Ni_1/6Mn_1/6O₂ cell showed a discharge capacity of 199 mAh g⁻¹ when cycled in the 2.7–4.6 V potential range while the best cycling performances were recorded when the upper cut off is fixed at 4.5 V. Structural changes in Li_xCo_2/3Ni_1/6Mn_1/6O₂ with lithium electrochemical de-intercalation were studied using X-ray diffraction. This study clearly shows the existence of a solid solution domain in the 0.1 < x < 1.0 composition range while for x = 0.1, a new phase appears explaining the decrease of the electrochemical performance when the cell is cycled at high upper cut off voltage.     

The effect of Al(OH)3 coating on the Li[Li0.2Ni0.2Mn0.6]O2 cathode material for lithium secondary battery

Layered Li[Li_0.2Ni_0.2Mn_0.6]O₂ powder was modified by coating its surface with amorphous Al(OH)₃. Energy dispersive spectroscopy (EDS) showed that nano-sized Al(OH)₃ powders were homogeneously dispersed in the parent Li[Li_0.2Ni_0.2Mn_0.6]O₂ powders. Al(OH)₃ coated Li[Li_0.2Ni_0.2Mn_0.6]O₂ exhibited an greater retention capacity at higher rates compared to uncoated Li[Li_0.2Ni_0.2Mn_0.6]O₂. The low area specific impedance (ASI) value of the Al(OH)₃ is the major factor for its higher rate performance. The 1.4 wt.% Al(OH)₃ coated sample had an impedance of 41 Ω cm² while uncoated Li[Li_0.2Ni_0.2Mn_0.6]O₂ had a 57 Ω cm² at 30-80% state of charge. Electrochemical impedance spectroscopy (EIS) also showed that the Al(OH)₃ coated sample had a lower charge transfer resistance (R_ct) than the uncoated sample. Differential scanning calorimetry (DSC) analysis showed that Al(OH)₃ coating improved the thermal stability. Al(OH)₃ coating increased the onset temperature of thermal decomposition and reduced the amount of heat for the exothermic peak.     

Characterization of high tap density Li[Ni1/3Co1/3Mn1/3]O2 cathode material synthesized via hydroxide co-precipitation

Li[Ni_1/3Co_1/3Mn_1/3]O₂ cathode material for lithium ion batteries was prepared by mixing metal hydroxide, (Ni_1/3Co_1/3Mn_1/3)(OH)₂, with 6% excess LiOH followed by calcinations. The (Ni_1/3Co_1/3Mn_1/3)(OH)₂ with secondary particle of about 12 μm was prepared by hydroxide co-precipitation. The tap density of the obtained Li[Ni_1/3Co_1/3Mn_1/3]O₂ powder was 2.56 ± 0.21 g cm⁻³. The powder was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), particle size distribution (PSD) and galvanostatic charge-discharge cycling. The XRD pattern of Li[Ni_1/3Co_1/3Mn_1/3]O₂ revealed a well ordered hexagonal layered structure with low cation mixing. Secondary particles with size of 13-14 μm and primary particles with size of about 1 μm can be identified from the SEM observations. In the voltage range of 2.8-4.3 V, the initial discharge capacity of the Li[Ni_1/3Co_1/3Mn_1/3]O₂ electrode was 166.6 mAh g⁻¹, and 96.5% of the initial capacity was retained after 50 charge-discharge cycling.