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.     

Preparation and electrochemical characteristics of LiNi1/3Mn1/3Co1/3O2 coated with metal oxides coating

LiNi_1/3Mn_1/3Co_1/3O₂ prepared by a spray drying method exhibited poor cyclic performance when it was operated at rates of 0.5C and 2C in 3–4.6 V. A metal oxide (ZrO₂, TiO₂, and Al₂O₃) coating (3 wt%) could effectively improve its cyclic performance at both 0.5C and 2C. Electrochemical impedance spectroscopy (EIS) studies suggested that both the surface resistance and the charge transfer resistance of the bare LiNi_1/3Mn_1/3Co_1/3O₂ significantly increase after 100 cycles, whose origin is mainly related to the change in both the particle surface and electrode morphologies. The presence of a thin metal oxide layer could remarkably suppress the increase in the total resistance (sum of the surface resistance and the charge transfer resistance), which was attributed to the improvement in good cyclic performances.     

Influence of lithium content on high rate cycleability of layered Li1+xNi0.30Co0.30Mn0.40O2 cathodes for high power lithium-ion batteries

Layered Li_1+xNi_0.30Co_0.30Mn_0.40O₂ (x = 0, 0.05, 0.10, 0.15) materials have been synthesized using citric acid assisted sol-gel method. The materials with excess lithium showed distinct differences in the structure and the charge and discharge characteristics. The rate capability tests were performed and compared on Li_1+xNi_0.30Co_0.30Mn_0.40O₂ (x = 0, 0.05, 0.10, 0.15) cathode materials. Among these materials, Li_1.10Ni_0.30Co_0.30Mn_0.40O₂ cathode demonstrated higher discharge capacity than that of the other cathodes. Upon extended cycling at 1C and 8C, Li_1.10Ni_0.30Co_0.30Mn_0.40O₂ showed better capacity retention when compared to other materials with different lithium content. Li_1.10Ni_0.30Co_0.30Mn_0.40O₂ exhibited 93 and 90% capacity retention where as Li_1.05Ni_0.30Co_0.30Mn_0.40O₂, Li_1.15Ni_0.30Co_0.30Mn_0.40O₂, and Li_1.00Ni_0.30Co_0.30Mn_0.40O₂ exhibited only 84, 71, and 63% (at 1C), and 79, 66 and 40% (at 10C) capacity retention, respectively, after 40 cycles. The enhanced high rate cycleability of Li_1.10Ni_0.30Co_0.30Mn_0.40O₂ cathode is attributed to the improved structural stability due to the formation of appropriate amount of Li₂MnO₃-like domains in the transition metal layer and decreased Li/Ni disorder (i.e., Ni content in the Li layer).     

De-intercalation of LixCo0.8Mn0.2O2: A magnetic approach

Samples of LiCo_0.8Mn_0.2O₂ were synthesized by a wet-chemical method using citric acid as a chelating agent, and were characterized by various physical techniques. Powders adopted the α-NaFeO₂ layered structure and were analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and regarding their magnetic properties. Transmission Electron Microscope (TEM) revealed particles with a mean size of 100 nm. Partial chemical delithiation was carried out by using an oxidizing agent. We observe that the material has ability to free lithium ions from its structure by this chemical process, which is analogous to the first step of the charge transfer process in an electrochemical cell. The rate of delithiation is determined independently by magnetic measurements and by the Rietveld refinement of the XRD spectra. Both the concentration of Mn³⁺-Mn⁴⁺ pairs and that of Mn⁴⁺-Mn⁴⁺ pairs formed in the delithiation process have been determined, together with that of the Mn³⁺-Mn³⁺ pairs. It shows that magnetic measurements are able to probe the distribution of Mn³⁺ and Mn⁴⁺ with more details than other techniques. The results are consistent with FTIR spectra, and indicate a random distribution of the Li ions that are removed from the matrix upon delithiation, which then undergo a diffusion process. Testing the material as cathode in lithium batteries revealed about 170 mAh g⁻¹ capacity, with a lower polarization and a high columbic efficiency, emphasizing the possibility of using this material as a cathode in Li-ion batteries.     

Aging of LiNi1/3Mn1/3Co1/3O2 cathode material upon exposure to H2O

LiNi_1/3Mn_1/3Co_1/3O₂ compound was successfully synthesized by the co-precipitation method. The effect of H₂O on LiNi_1/3Mn_1/3Co_1/3O₂ in humid atmosphere was investigated by structural, magnetic and electrochemical analysis, and Raman spectroscopy. The consequence is that immersion of LiNi_1/3Mn_1/3Co_1/3O₂ to H₂O and exposure of LiNi_1/3Mn_1/3Co_1/3O₂ to humid atmosphere (ambient atmosphere, 20 °C, 50% relative humidity) led to a rapid attack that manifests itself by the delithiation of the surface layer of the particles and the concomitant formation of LiOH and Li₂ CO₃ at the surface. This aging process occurred during the first few minutes, then it is saturated, and the thickness of the surface layer at saturation is 10 nm. After aging, an initial discharge capacity of 139 mAh/g was delivered at 1C-rate in the cut-off voltage of 3.0-4.3 V. About 95% of its initial capacity was retained after 30 cycles.     

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.     

Preparation and electrochemical properties of layer-structured LiNi1/3Co1/3Mn1/3−yAlyO2

Layer-structured LiNi_1/3Co_1/3Mn_1/3−yAl_yO₂ has been synthesized via a sol–gel method. The lattice constants of LiNi_1/3Co_1/3Mn_1/3−yAl_yO₂ decrease with the concentration of aluminum ions. XANES analysis further confirms that the valence of cobalt ion is 3+, and that of Ni is between 2+ and 3+ in LiNi_1/3Co_1/3Mn_1/3−yAl_yO₂. With doping aluminum ions, the redox centers for the electrochemical reaction change from nickel ions alone to both nickel and cobalt ions. The amounts of de-intercalatable lithium ions are affected by the concentration of aluminum ions; however, the extracting efficiency of lithium ions is improved by doping aluminum ions. Among all the samples, LiNi_1/3Co_1/3Mn_0.23Al_0.1O₂ exhibits the best capacity retention and the least irreversible capacity.     

Effect of an organic additive on the cycling performance and thermal stability of lithium-ion cells assembled with carbon anode and LiNi1/3Co1/3Mn1/3O2 cathode

A small amount of thiophene or ethylene dioxythiophene (EDOT) is introduced into the liquid electrolyte of lithium-ion cells as an additive. These organic additives are electrochemically oxidized to form a thin conductive polymer film on the surface of the cathode at high potential. With the liquid electrolyte containing different additives, the lithium-ion cells composed of carbon anode and LiNi_1/3Co_1/3Mn_1/3O₂ cathode are assembled, and their cycling performances are evaluated. Adding small amounts of thiophene or EDOT to the liquid electrolyte is found to reduce the interfacial resistance in the cells and thus the cells containing an organic additive exhibit less capacity fading and better high-rate performance. Differential scanning calorimetric studies show that the thermal stability of the charged Li_1−xNi_1/3Co_1/3Mn_1/3O₂ cathode is also enhanced in the presence of an organic additive.     

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.     

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.     

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.     

Investigation of LiNi1/3Co1/3Mn1/3O2 cathode particles after 300 discharge/charge cycling in a lithium-ion battery by analytical TEM

Using analytical transmission electron microscopy (TEM) techniques reveal a zigzag layer on surface of the cycled particles of LiNi_1/3Co_1/3Mn_1/3O₂ cathode after 300 discharge/charge cycles. The Ni, Mn content in the zigzag layer of the cycled particle has decreased rapidly from interior to edge of the zigzag layer of the cycled particles. The structure of LiNi_1/3Co_1/3Mn_1/3O₂ oxide was gradually destructed from hexagonal cell with P3₁12 at interior region to fcc lattice of α-NaFeO₂ at edge of the zigzag layer of the cycled particles. These experimental data provide the compositional and structural origins of the capacity decrease in the Li-ion battery.     

Solution combustion synthesis of layered LiNi0.5Mn0.5O2 and its characterization as cathode material for lithium-ion cells

LiNi_0.5Mn_0.5O₂, a promising cathode material for lithium-ion batteries, is synthesized by a novel solution-combustion procedure using acenaphthene as a fuel. The powder X-ray diffraction (XRD) pattern of the product shows a hexagonal cell with a = 2.8955 Å and c = 14.1484 Å. Electron microscopy investigations indicate that the particles are of sub-micrometer size. The product delivers an initial discharge capacity of 161 mAh g⁻¹ between 2.5 and 4.6 V at a 0.1 C rate and could be subjected to more than 50 cycles. The electrochemical activity is corroborated with cyclic voltammetric (CV) and electrochemical impedance data. The preparative procedure presents advantages such as a low cation mixing, sub-micron particles and phase purity.     

Study of the surface modification of LiNi1/3Co1/3Mn1/3O2 cathode material for lithium ion battery

The surface of LiNi_1/3Co_1/3Mn_1/3O₂ (LNMCO) particles has been studied for material synthesized at 900 °C by a two-step process from a mixture of LiOH·H₂O and metal oxalate [(Ni_1/3Co_1/3Mn_1/3)C₂O₄] obtained by co-precipitation. Samples have been characterized by X-ray diffraction (XRD), high-resolution transmission electron microscope (HRTEM), Raman scattering (RS) spectroscopy, and magnetic measurements. We have investigated the effect of the heat treatment of particles at 600 °C with organic substances such as sucrose and starch. HRTEM images and RS spectra indicate that the surface of particles has been modified. The annealing does not lead to any carbon coating but it leads to the crystallization of the thin disordered layer on the surface of LiNi_1/3Co_1/3Mn_1/3O₂. The beneficial effect has been tested on the electrochemical properties of the LiNi_1/3Co_1/3Mn_1/3O₂ cathode materials. The capacity at 10C-rate is enhanced by 20% for post-treated LNMCO particles at 600 °C for half-an-hour.     

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.     

Fine-sized LiNi0.8Co0.15Mn0.05O2 cathode powders prepared by combined process of gas-phase reaction and solid-state reaction methods

The Ni-rich precursor powders with spherical shape and filled morphologies were prepared by spray pyrolysis from the spray solution with citric acid, ethylene glycol and a drying control chemical additive. The precursor powders with controlled morphologies formed the LiNi_0.8Co_0.15Mn_0.05O₂ cathode powders with spherical shape and fine size by solid-state reaction with lithium hydroxide. However, the cathode powders prepared from the spray solution without additives had irregular morphologies and were large in size. The precursor powders with hollow and porous morphologies formed cathode powders with irregular and aggregated morphologies. The composition ratios of the nickel, cobalt and manganese components were maintained in the as-prepared, precursor and cathode powders. The initial discharge capacity of the LiNi_0.8Co_0.15Mn_0.05O₂ cathode powders with spherical shape and fine size tested at a temperature of 55 °C under a constant current density of 0.5 C was 215 mAh g⁻¹. The discharge capacity of the LiNi_0.8Co_0.15Mn_0.05O₂ cathode powders decreased to 81% of the initial value after 30 cycles.     

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.     

Hydrothermal synthesis of SnO2–V2O5 mixed oxide and electrochemical screening of carbon nano-tubes (CNT), V2O5, V2O5–CNT,and SnO2–V2O5–CNT electrodes for supercapacitor applications

Nano-scaled SnO₂–V₂O₅ mixed oxide is synthesized by a hydrothermal method in an autoclave. For comparative evaluation, V₂O₅ single oxide is prepared by a conventional process from ammonium vanadate. The capacitive behaviour of the following electrodes is studied by cyclic voltammetry in 0.1 M KCl solutions: carbon nano-tubes (CNT), V₂O₅, V₂O₅–CNT, and SnO₂–V₂O₅–CNT. At a scan rate of 100 mV s⁻¹, the SnO₂–V₂O₅–CNT electrode provides the best performance, viz., 121.4 F g⁻¹. The nano-scaled mixed oxide is characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and Raman spectra.     

Structural and thermal stabilities of layered Li(Ni1/3Co1/3Mn1/3)O2 materials in 18650 high power batteries

The structural and thermal stabilities of the layered Li(Ni_1/3Co_1/3Mn_1/3)O₂ cathode materials under high rate cycling and abusive conditions are investigated using the commercial 18650 Li(Ni_1/3Co_1/3Mn_1/3)O₂/graphite high power batteries. The Li(Ni_1/3Co_1/3Mn_1/3)O₂ materials maintain their layered structure even when the power batteries are subjected to 200 cycles with 10 C discharge rate at temperatures of 25 and 50 °C, whereas their microstructure undergoes obvious distortion, which leads to the relatively poor cycling performance of power batteries at high charge/discharge rates and working temperature. Under abusive conditions, the increase in the battery temperature during overcharge is attributed to both the reactions of electrolyte solvents with overcharged graphite anode and Li(Ni_1/3Co_1/3Mn_1/3)O₂ cathode and the Joule heat that results from the great increase in the total resistance (R_cell) of batteries. The reactions of fully charged Li(Ni_1/3Co_1/3Mn_1/3)O₂ cathodes and graphite anodes with electrolyte cannot be activated during short current test in the fully charged batteries. However, these reactions occur at around 140 °C in the fully charged batteries during oven test, which is much lower than the temperature of about 240 °C required for the reactions outside batteries.     

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.