Effect of carbon coating on LiNi1/3Mn1/3Co1/3O2 cathode material for lithium secondary batteries

Amorphous carbon is coated on LiNi_1/3Mn_1/3Co_1/3O₂ cathode material for lithium batteries. The carbon-coated material shows improved thermal stability and electrochemical performance compared with bare material.     

Effect of Ag additive on the performance of LiNi1/3Co1/3Mn1/3O2 cathode material for lithium ion battery

The LiNi_1/3Co_1/3Mn_1/3O₂/Ag composite used for cathode material of lithium ion battery was prepared by thermal decomposition of AgNO₃ added to commercial LiNi_1/3Co_1/3Mn_1/3O₂ powders to improve the electrochemical performance of LiNi_1/3Mn_1/3Co_1/3O₂. Structure and morphology analysis showed that Ag particles were dispersed on the surface of LiNi_1/3Co_1/3Mn_1/3O₂ instead of entering the crystal structure. The results of charge–discharge tests showed that Ag additive could improve the cycle performance and high-rate discharge capability of LiNi_1/3Mn_1/3Co_1/3O₂. Extended analysis indicated that Ag was unstable in the commercial electrolyte at high potential. The improved electrochemical performance caused by Ag additive was associated not only with the enhancement of electrical conductivity of the material and the lower polarization of the cell, but also with the increased “c” parameter of LiNi_1/3Mn_1/3Co_1/3O₂ after repeated charge/discharge cycles and the compact and protective SEI layer formed on the surface of LiNi_1/3Mn_1/3Co_1/3O₂.     

Preparation of spherical LiNi0.80Co0.15Mn0.05O2 lithium-ion cathode material by continuous co-precipitation

Micro-spherical Ni_0.80Co_0.15Mn_0.05(OH)₂ precursors with a narrow size-distribution and high tap-density are prepared successfully by continuous co-precipitation of the corresponding metal salt solutions using NaOH and NH₄OH as precipitation and complexing agents. LiNi_0.80Co_0.15Mn_0.05O₂ is then prepared as a lithium battery cathode from this precursor by the introduction of LiOH·H₂O. The pH and NH₃:metal molar ratio show significant effects on the morphology, microstructure and tap-density of the prepared Ni_0.80Co_0.15Mn_0.05(OH)₂ and the R values and I(0 0 3)/I(1 0 4) ratio of lithiated LiNi_0.80Co_0.15Mn_0.05O₂. Spherical LiNi_0.80Co_0.15Mn_0.05O₂ prepared under optimum conditions reveals a hexagonally ordered, layered structure without cation mixing and an initial charging capacity of 176 mAhg⁻¹. More than 91% of the capacity is retained after 40 cycles at the 1 C rate in a cut-off voltage range of 4.3-3.0 V.     

Structural and electrochemical properties of LiNi1/3Co1/3Mn1/3O2: Calcination temperature dependence

The structure of the layered LiNi_1/3Co_1/3Mn_1/3O₂ has been investigated by powder X-ray diffraction and electron diffraction, and the relationship of the calcination temperature with the crystal structure, morphology and electrochemical properties has been studied. All the unit cell parameters increase monotonically with increasing the calcination temperature. Some of the [00.1] zone electron diffraction patterns for the sample calcined at higher temperature than 1000 °C show extra spots indicating the 2 × 2 ordering in the basal triangular lattice. These results indicate that the high temperature calcination leads to the formation of vacancies in the transition metal layers with the spinel-like ordering. The calcination at higher temperature lowers the specific capacities and degrades the cycle performances, while the packing density of the powder is increased by the sintering. The optimum calcination temperature is 900 °C in order to obtain the electrochemically active and dense packed oxide particles. The decrease of Li composition leads to coprecipitation of the spinel-like second phase in the range of 0.742 ≤ x ≤ 0.884 for Li_xNi_1/3Co_1/3Mn_1/3O₂, when calcined at 900 °C. The Li-deficient samples show the worse electrochemical properties similarly to the stoichiometric samples calcined at high temperature. For the Li-excess samples, no impurity phase has been detected and their cycle performances are improved.     

Synthesis and electrochemical studies of the 4 V cathode, Li(Ni2/3Mn1/3)O2

Layered Li(Ni_2/3Mn_1/3)O₂ compounds are prepared by freeze-drying, mixed carbonate and molten salt methods at high temperature. The phases are characterized by X-ray diffraction, Rietveld refinement, and other methods. Electrochemical properties are studied versus Li-metal by charge–discharge cycling and cyclic voltammetry (CV). The compound prepared by the carbonate route shows a stable capacity of 145 (±3) mAh g⁻¹ up to 100 cycles in the range 2.5–4.3 V at 22 mA g⁻¹. In the range 2.5–4.4 V at 22 mA g⁻¹, the compound prepared by molten salt method has a stable capacity of 135 (±3) mAh g⁻¹ up to 50 cycles and retains 96% of this value after 100 cycles. Capacity-fading is observed in all the compounds when cycled in the range 2.5–4.5 V. All the compounds display a clear redox process at 3.65–4.0 V that corresponds to the Ni^2+/3+–Ni^3+/4+ couple.     

The electrochemical property of ZrFx-coated Li[Ni1/3Co1/3Mn1/3]O2 cathode material

Electrochemical and thermal properties of pristine and ZrF_x-coated Li[Ni_1/3Co_1/3Mn_1/3]O₂ cathode materials are compared. The hydrothermal method is introduced for the fabrication of a uniform coating layer. The formation of a compact coating layer on the surface of pristine powder is observed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). From TEM-EDS and XPS analysis, it is inferred that the coating layer is ZrO_xF_y (zirconium oxyfluoride) form. The coated Li[Ni_1/3Co_1/3Mn_1/3]O₂ electrodes have better rate capability and cyclic performance at high temperature compared with the pristine electrode. The thermal stability of the Li[Ni_1/3Co_1/3Mn_1/3]O₂ electrode is also enhanced by the ZrF_x coating. Such enhancements are due to the presence of a stable coating layer, which effectively suppresses the chemical instability ascribed to surface reaction between electrode and electrolyte.     

Preparation and electrochemical characterization of single-crystalline spherical LiNi1/3Co1/3Mn1/3O2 powders cathode material for Li-ion batteries

LiNi_1/3Co_1/3Mn_1/3O₂ has aroused much interest as a new generation of cathode material for Li-ion batteries, due to its great advantages in capacity, stability, low cost and low toxicity, etc. Here we report a novel single-crystalline spherical LiNi_1/3Co_1/3Mn_1/3O₂ material that is prepared by a convenient rheological phase reaction route. The X-ray powder diffraction, scanning electron microscopy and transmission electron microscopy indicate that the particles are highly dispersed with spherical morphologies and diameters of about 1-4 μm, and more interestingly, they show a perfect single-crystalline nature, which is not usual according to the crystal growth theories and may bring extra benefits to applications. Electrochemical tests show good performance of the material in both the capacity and cycling stability as cathode material in a model cell.     

Studies on the low-heating solid-state reaction method to synthesize LiNi1/3Co1/3Mn1/3O2 cathode materials

The low-heating solid-state method has been adopted to synthesize LiNi_1/3Co_1/3Mn_1/3O₂ materials. The final product, with homogeneous phase and smooth crystals indicated by XRD and SEM results, can be synthesized at 700 °C, much lower than the synthesis temperatures of co-precipitation method. The reaction process and microstructure of precursor has been investigated by IR spectrum. By comparative studies with the mixture of CH₃COOLi and (Ni, Co, Mn)(C₂O₄), it is testified that the precursor is homogeneous, rather than a mixture. The decomposition process and the reaction energy have been studied to investigate the reaction mechanism of the precursor when heated at high temperature. The as-synthesized LiNi_1/3Co_1/3Mn_1/3O₂ exhibits excellent electrochemical properties, exhibiting initial specific capacity of 167 mAh g⁻¹ with stable cyclic performance.     

On the LiNi0.2Mn0.2Co0.6O2 positive electrode material

Layered LiNi_0.2Mn_0.2Co_0.6O₂ phase, belonging to a solid solution between LiNi_1/2Mn_1/2O₂ and LiCoO₂ most commercialized cathodes, was prepared via the combustion method at 900 °C for a short time (1 h). Structural, electrochemical and magnetic properties of this material were investigated. Rietveld analysis of the XRD pattern shows this compound as having the α-NaFeO₂ type structure (S.G. R-3m; a = 2.8399(2) ?; c = 14.165(1) ?) with almost none of the well-known Li/Ni cation disorder. SQUID measurements clearly indicate that the studied compound consists of Ni²⁺, Co³⁺ and Mn⁴⁺ ions in the crystal structure. X-ray analysis of the chemically delithiated Li_xNi_0.2Mn_0.2Co_0.6O₂ phases reveals that the rhombohedral symmetry was maintained during Li-extraction, confirmed by the monotonous variation of the potential-composition curve of the Li//Li_xNi_0.2Mn_0.2Co_0.6O₂ cell. LiNi_0.2Mn_0.2Co_0.6O₂ cathode has a discharge capacity of ∼160 mAh g⁻¹ in the voltage range 2.7-4.3 V corresponding to the extraction/insertion of 0.6 lithium ion with very low polarization. It exhibits a stable capacity on cycling and good rate capability in the rate range 0.2-2 C. The almost 2D structure of this cathode material, its good electrochemical performances and its relatively low cost comparing to LiCoO₂, make this material very promising for applications.     

Synthesis of LiNi1/3Co1/3Mn1/3O2 as a cathode material for lithium battery by the rheological phase method

LiNi_1/3Co_1/3Mn_1/3O₂ is prepared by a rheological phase method. Homogeneous precursor derived from this method is calcined at 800 °C for 20 h in air, which results in the impressive differences in the morphology properties and electrochemical behaviors of LiNi_1/3Co_1/3Mn_1/3O₂ in contrast to that obtained by a solid-state method. The microscopic structural features of LiNi_1/3Co_1/3Mn_1/3O₂ are investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD). The electrochemical properties of LiNi_1/3Co_1/3Mn_1/3O₂ are carried out by charge–discharge cycling test. All experiments show that the microscopic structural features and the morphology properties are deeply related with the electrochemical performances. The obtained results suggest that the rheological phase method may become an effective route to prepare LiNi_1/3Co_1/3Mn_1/3O₂ cathode materials for lithium battery.     

Surface modification of Li[Ni0.3Co0.4Mn0.3]O2 cathode by Li-La-Ti-O coating

A Li[Ni_0.3Co_0.4Mn_0.3]O₂ cathode is modified by applying a Li-La-Ti-O coating using the hydrothermal method. The coated Li[Ni_0.3Co_0.4Mn_0.3]O₂ is characterized by X-ray diffraction analysis, scanning electron microscopy, energy-dispersive spectrometry, transmission electron microscopy, and differential scanning calorimetry. The Li-La-Ti-O coating layer is formed as crystalline (perovskite structure) or amorphous phase depending on the heating temperature. The Li-La-Ti-O coated Li[Ni_0.3Co_0.4Mn_0.3]O₂ electrode has better rate capability than the pristine electrode. In particular, the rate capability is significantly associated with heating temperature; this is probably due to the phase of the coating layer. It appears that the Li-La-Ti-O coating of amorphous phase is superior to that of crystalline phase for obtaining enhanced rate capability of the coated samples. The thermal stability and cyclic performance of the Li[Ni_0.3Co_0.4Mn_0.3]O₂ electrode are also improved by Li-La-Ti-O coating. These improvements indicate that the Li-La-Ti-O coating is effective in suppressing the chemical and structural instabilities of Li[Ni_0.3Co_0.4Mn_0.3]O₂.     

Preparation and electrochemical properties of Li[Ni1/3Co1/3Mn1−x/3Zrx/3]O2 cathode materials for Li-ion batteries

Layer-structured Zr doped Li[Ni_1/3Co_1/3Mn_1−x/3Zr_x/3]O₂ (0 ≤ x ≤ 0.05) were synthesized via slurry spray drying method. The powders were characterized by XRD, SEM and galvanostatic charge/discharge tests. The products remained single-phase within the range of 0 ≤ x ≤ 0.03. The charge and discharge cycling of the cells showed that Zr doping enhanced cycle life compared to the bare one, while did not cause the reduction of the discharge capacity of Li[Ni_1/3Co_1/3Mn_1/3]O₂. The unchanged peak shape in the differential capacity versus voltage curve suggested that the Zr had the effect to stabilize the structure during cycling. More interestingly, the rate capability was greatly improved. The sample with x = 0.01 presented a capacity of 160.2 mAh g⁻¹ at current density of 640 mA g⁻¹(4 C), corresponding to 92.4% of its capacity at 32 mA g⁻¹(0.2 C). The favorable performance of the doped sample could be attributed to its increased lattice parameter.     

Synthesis and electrochemical studies on Al2O3 coated LiNi0.5Co0.44Fe0.06VO4 for lithium ion batteries

LiNi_0.5Co_0.44Fe_0.06VO₄ cathode material has been synthesized by a citric acid:polyethylene glycol polymeric method at 723 K for 5 h in air. The surface of the LiNi_0.5Co_0.44Fe_0.06VO₄ was coated with various wt.% of Al₂O₃ by a wet chemical procedure and heat treated 873 K for 2 h in air. The samples were characterized by XRD, FTIR, SEM, and TEM techniques. XRD patterns expose that the complete crystalline phase occurred at 723 K and there was no indication of new peaks for the coated samples. FTIR spectra show that the complete removal of organic residues and the formation of LiNi_0.5Co_0.44Fe_0.06VO₄. TG/DTGA results reveal that the formation of LiNi_0.5Co_0.44Fe_0.06VO₄ occurred between 480 and 670 K and the complete crystalline occurred at 723 K. SEM micrographs show the various morphological stages of the polymeric intermediates. TEM micrographs of the pristine LiNi_0.5Co_0.44Fe_0.06VO₄ reveal that the particle size ranged from 130 to 150 nm and Al₂O₃ coating on the fine particles was compact and had an average thickness of about 15 nm. The charge–discharge experiments were carried out between 2.8 and 4.9 V (versus Li) at a current rate of 0.15 C. The 1.0 wt.% Al₂O₃ coated sample had the best electrochemical performance, with an initial capacity of 65 mAh g⁻¹ and capacity retention of 60% after 50 cycles. The electrochemical impedance behavior suggests that the failure of pristine cathode performance is associated with an increase in the impedance growth on the surface of the cathode material upon continuous cycling.     

Cycle life improvement of ZrO2-coated spherical LiNi1/3Co1/3Mn1/3O2 cathode material for lithium ion batteries

A modified synthesis process was developed based on co-precipitation method followed by spray drying process. In this process, a spherical shaped (Co_1/3Ni_1/3Mn_1/3)(OH)₂ precursor was synthesized by co-precipitation and pre-heated at 500 °C to form a high structural stability spinel (CoNiMn)O₄ to maintain its shape for further processing. The spherical LiNi_1/3Co_1/3Mn_1/3O₂ was then prepared by spray drying process using spherical spinel (CoNiMn)O₄. LiNi_1/3Co_1/3Mn_1/3O₂ powders were then modified by coating their surface with a uniform and nano-sized layer of ZrO₂. The ZrO₂-coated LiNi_1/3Co_1/3Mn_1/3O₂ material exhibited an improved rate capability and cycling stability under a high cut-off voltage of 4.5 V. X-ray diffraction (XRD) measurements revealed that the material had a well-ordered layered structure and Zr was not doped into the LiNi_1/3Co_1/3Mn_1/3O₂. Electrochemical impedance spectroscopy measurements showed that the coated material has stable cell resistance regardless of cycle number. The interrupt charging/discharging test indicated that the ZrO₂ coating can suppress the polarization effects during the charging and discharging process. From these results, it is believed that the improved cycling performance of ZrO₂-coated LiNi_1/3Co_1/3Mn_1/3O₂ is attributed to the ability of ZrO₂ layer in preventing direct contact of the active material with the electrolyte resulting in a decrease of electrolyte decomposition reactions.     

A novel layered material of LiNi0.32Mn0.33Co0.33Al0.01O2 for advanced lithium-ion batteries

A novel layered material of LiNi_0.32Mn_0.33Co_0.33Al_0.01O₂ with α-NaFeO₂ structure is synthesized by sol-gel method. X-ray diffraction (XRD) shows that the cation mixing in the Li layers of it is decreased. In addition, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) are employed to characterize the reaction of lithium-ion insertion and extraction from materials. The results indicate that the structure of LiNi_0.32Mn_0.33Co_0.33Al_0.01O₂ is more stable than that of the LiNi_0.33Mn_0.33Co_0.33O₂. The capacity retention of LiNi_0.33Mn_0.33Co_0.33O₂ after 40 cycles at 2.0 C is only 89.9%, however, that of the LiNi_0.32Mn_0.33Co_0.33Al_0.01O₂ is improved to 97.1%. The capacity of the LiNi_0.32Mn_0.33Co_0.33Al_0.01O₂ at 4.0 C remains 71.8% of the capacity at 0.2 C, while that of the LiNi_0.33Mn_0.33Co_0.33O₂ is only 54.3%. EIS measurement reveals that the increase in the charge transfer resistance during cycling is suppressed in the LiNi_0.32Mn_0.33Co_0.33Al_0.01O₂ material.     

Microemulsion preparation and electrochemical characteristics of LiNi1/3Co1/3Mn1/3O2 powders

Layer-structured LiNi_1/3Co_1/3Mn_1/3O₂ was successfully synthesized via a reverse microemulsion (RμE) route. Well-crystallized nanosized (around 45 nm) powders were obtained with calcination at 800 °C. The Rietveld refinement data revealed low degree of cationic displacement in the obtained powders. Within the voltage range of 2.5–4.5 V, the microemulsion-derived LiNi_1/3Co_1/3Mn_1/3O₂ delivered 187.2 and 195.5 mAh g⁻¹ at room temperature and 55 °C, respectively. The prepared powders were found to exhibit low irreversible capacity and good capacity retention. Microemulsion-derived LiNi_1/3Co_1/3Mn_1/3O₂ demonstrated better rate capability than the solid-state derived samples, owing to the reduced particle size and increased surface area. Once the upper cut-off voltage reached 4.6 V, the capacity faded more rapidly than in other operation potential ranges. In this study, the microemulsion process effectively improved the electrochemical characteristics of LiNi_1/3Co_1/3Mn_1/3O₂. This soft chemical route possesses a great potential for synthesizing other types of cathode materials with multiple cations.     

Synthesis and electrochemical properties of layered LiNi2/3Sb1/3O2

LiNi_2/3Sb_1/3O₂ has been prepared by ion-exchange from NaNi_2/3Sb_1/3O₂. Powder X-ray diffraction (XRD) and single crystal electron diffraction by transmission electron microscopy (TEM) of the material indicate that it is isostructural with α-NaFeO₂. Electrochemical test shows that the reversible capacity for Li intercalation and deintercalation drops rapidly with the number of times cycled. Both experimental evidences and first principles calculations point to the migration of nickel as the reason for the poor capacity retention.     

Enhanced electrochemical properties of Li(Ni0.4Co0.3Mn0.3)O2 cathode by surface modification using Li3PO4-based materials

The surface of a commercial Li[Ni_0.4Co_0.3Mn_0.3]O₂ cathode is modified using Li₃PO₄-based coating materials. The electrochemical properties of the coated materials are investigated as a function of the pH value of the coating solution and the composition of coating materials. The Li₃PO₄ coating solution with pH 2 is found to be favorable for the formation of stable coating layers having enhanced electrochemical properties. The Li₃PO₄, Li_1.5PO₄, and PO₄ coating layers are formed as amorphous phases. However, the Li_3−xNi_x/2PO₄ coating layers are composed of small particles with a crystalline phase covered with an amorphous phase. Li₃PO₄ and Li_1.5PO₄ coatings considerably enhance the rate capability of the Li[Ni_0.4Co_0.3Mn_0.3]O₂ electrode. In contrast, the Li_3−xNi_x/2PO₄ coating material, which contained Ni, has an inferior rate capability compared to the Li_xPO₄ series (x = 1.5 and 3), although the LiNiPO₄-coated electrode shows a better rate capability than a pristine one. Li₃PO₄-based coating materials are effective at enhancing the cyclic performance of the electrode in the voltage range of 3.0-4.8 V. DSC analysis also confirms the improved thermal stability attained by coating the cathode with Li₃PO₄-based materials.     

Morphology and electrochemical performance of Li[Ni1/3Co1/3Mn1/3]O2 cathode material by a slurry spray drying method

The spherical Li[Ni_1/3Co_1/3Mn_1/3]O₂ powders with appropriate porosity, small particle size and good particle size distribution were successfully prepared by a slurry spray drying method. The Li[Ni_1/3Co_1/3Mn_1/3]O₂ powders were characterized by XRD, SEM, ICP, BET, EIS and galvanostatic charge/discharge testing. The material calcined at 950 °C had the best electrochemical performance. Its initial discharge capacity was 188.9 mAh g⁻¹ at the discharge rate of 0.2 C (32 mA g⁻¹), and retained 91.4% of the capacity on going from 0.2 to 4 C rate. From the EIS result, it was found that the favorable electrochemical performance of the Li[Ni_1/3Co_1/3Mn_1/3]O₂ cathode material was primarily attributed to the particular morphology formed by the spray drying process which was favorable for the charge transfer during the deintercalation and intercalation cycling.     

A novel method for synthesis of layered LiNi1/3Mn1/3Co1/3O2 as cathode material for lithium-ion battery

The layered LiNi_1/3Mn_1/3Co_1/3O₂ materials with good crystalline are synthesized by a novel method of hydrothermal method followed by a short calcination process. The crystalline structure and morphology of the synthesized materials are characterized by XRD, SEM. Their electrochemical performances are evaluated by CV, EIS and galvonostatic charge/discharge tests. The material synthesized at 850 °C for 6 h shows the highest initial discharge capacity of 187.7 mAh g⁻¹ at 20 mA g⁻¹. And the capacity retention of 97.9% is maintained at the end of 40 cycles at 1.0 C. CV test reveals almost no shift of anodic and cathodic peaks after first cycle, which indicates good reversible deintercalation and intercalation of Li⁺ ions.