Electrochemical investigation of LiNi0.5Mn1.5O4 thin film intercalation electrodes

This work provides kinetic and transport parameters of Li-ion during its extraction/insertion into thin film LiNi_0.5Mn_1.5O₄ free of binder and conductive additive. Thin films of LiNi_0.5Mn_1.5O₄ (0.2 μm thick) were prepared on electronically conductive gold substrate utilizing the electrostatic spray deposition technique. High purity LiNi_0.5Mn_1.5O₄ thin film electrodes were observed with cyclic voltammetry, to exhibit very sharp peaks, high reversibility, and absence of the 4 V signal related to the Mn³⁺/Mn⁴⁺ redox couple. The electrode subjected to 100 CV cycles of charge/discharge delivered a capacity of 155 mAh g⁻¹ on the first cycle and sustained a good cycling behavior while retaining 91% of the initial capacity after 50 cycles. Kinetics and mass-transport of Li-ion extraction at LiNi_0.5Mn_1.5O₄ thin film electrode were investigated by means of electrochemical impedance spectroscopy. The apparent chemical diffusion coefficient (D_app) value determined from EIS measurements changed depending on the electrode potential in the range of 10⁻¹⁰-10⁻¹² cm² s⁻¹. The D_app profile shows two minimums at the potential values close to the peak potentials of the corresponding cyclic voltammogram.     

Synthesis and electrochemical characterization of LiNi0.5Mn1.5O4 by one-step precipitation method with ammonium carbonate as precipitating agent

Spinel LiNi_0.5Mn_1.5O₄ materials are synthesized by one-step precipitation method. Ammonium carbonate is used as the precipitating agent to obtain a more precise feed ratio without recourse to traditional washing. After annealing at high temperature, the spherical particles become angular and show high levels of crystallinity. The synthesized samples are evaluated using powder X-ray diffraction, scanning electron microscopy, and electrochemical testing. The samples synthesized with different metal ion concentrations yield different morphologies and rate performances. The sample synthesized with 0.2 mol L⁻¹ gives the most uniform particle distribution and the best electrochemical performance. The specific discharge capacity values of the sample at 10 and 15 C are as high as 109.5 and 88.7 mAh g⁻¹, respectively. After the high-rate cycling, its discharge capacity at 0.2 C can be reverted to 97.67% of its initial capacity.     

Enhanced electrochemical performances of LiNi0.5Mn1.5O4 spinel via ethylene glycol-assisted synthesis

A simple and effective method, ethylene glycol-assisted co-precipitation method, has been employed to synthesize LiNi_0.5Mn_1.5O₄ spinel. As a chelating agent, ethylene glycol can realize the homogenous distributions of metal ions at the atomic scale and prevent the growth of LiNi_0.5Mn_1.5O₄ particles. XRD reveals that the prepared material is a pure-phase cubic spinel structure (Fd3m) without any impurities. SEM images show that it has an agglomerate structure with the primary particle size of less than 100 nm. Electrochemical tests demonstrate that the as-prepared LiNi_0.5Mn_1.5O₄ possesses high capacity and excellent rate capability. At 0.1 C rate, it shows a discharge capacity of 137 mAh g⁻¹ which is about 93.4% of the theoretical capacity (146.7 mAh g⁻¹). At the high rate of 5 C, it can still deliver a discharge capacity of 117 mAh g⁻¹ with excellent capacity retention rate of more than 95% after 50 cycles. These results show that the as-prepared LiNi_0.5Mn_1.5O₄ is a promising cathode material for high power Li-ion batteries.     

Ultrathin CeO2 coating for improved cycling and rate performance of Ni-rich layered LiNi0.7Co0.2Mn0.1O2 cathode materials

In this study, we have successfully coated the CeO₂ nanoparticles (CeONPs) layer onto the surface of the Ni-rich layered LiNi_0.7Co_0.2Mn_0.1O₂ cathode materials by a wet chemical method, which can effectively improve the structural stability of electrode. The X-ray powder diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS) are used to determine the structure, morphology, elemental composition and electronic state of pristine and surface modified LiNi_0.7Co_0.2Mn_0.1O₂. The electrochemical testing indicates that the 0.3?mol% CeO₂-coated LiNi_0.7Co_0.2Mn_0.1O₂ demonstrates excellent cycling capability and rate performance, the discharge specific capacity is 161.7?mA?h?g^?1 with the capacity retention of 86.42% after 100 cycles at a current rate of 0.5?C, compared to 135.7?mA?h?g^?1 and 70.64% for bare LiNi_0.7Co_0.2Mn_0.1O₂, respectively. Even at 5?C, the discharge specific capacity is still up to 137.1?mA?h?g^?1 with the capacity retention of 69.0%, while the NCM only delivers 95.5?mA?h?g^?1 with the capacity retention of 46.6%. The outstanding electrochemical performance is assigned to the excellent oxidation capacity of CeO₂ which can oxidize Ni²⁺ to Ni³⁺ and Mn³⁺ to Mn⁴⁺ with the result that suppress the occurrence of Li⁺/Ni²⁺ mixing and phase transmission. Furthermore, CeO₂ coating layer can protect the structure to avoid the occurrence of side reaction. The CeO₂-coated composite with enhanced structural stability, cycling capability and rate performance is a promising cathode material candidate for lithium-ion battery.     

Improvement of electrochemical properties of LiNi0.5Mn1.5O4 spinel prepared by radiated polymer gel method

LiNi_0.5Mn_1.5O₄ as a 4.7 V-class cathode material was prepared through the radiated polymer gel method that allowed homogeneous mixing of starting materials at the atomic scale. After calcinations of the polymer gels containing the metal salts at different temperatures from 750 to 1150 °C, powders of a pure LiNi_0.5Mn_1.5O₄ phase were obtained. X-ray diffraction and transmission electron microscopy were used to characterize the structures of the powders. Galvanostatic cell cycling and a simultaneous DC resistance measurement were performed on Li/LiNi_0.5Mn_1.5O₄ cells. It is found that the powder calcined at 950 °C shows the best electrochemical performance with the initial discharge capacity of 139 mAh g⁻¹ and 96% retention after 50 cycles. Adopting a slow cooling procedure for the powder calcination can increase the capacity of LiNi_0.5Mn_1.5O₄ at the 4.7 V plateau. Besides, a “w”-shape change of the DC resistance of Li/LiNi_0.5Mn_1.5O₄ cells is a good indication of the structural change of LiNi_0.5Mn_1.5O₄ electrode during charge and discharge courses.     

Spray-drying synthesized LiNi0.6Co0.2Mn0.2O2 and its electrochemical performance as cathode materials for lithium ion batteries

Layered LiNi_0.6Co_0.2Mn_0.2O₂ materials were synthesized at different sintering temperatures using spray-drying precursor with molar ratio of Li/Me = 1.04 (Me = transition metals). The influences of sintering temperature on crystal structure, morphology and electrochemical performance of LiNi_0.6Co_0.2Mn_0.2O₂ materials have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and charge-discharge test. As a result, material synthesized at 850 °C has excellent electrochemical performance, delivering an initial discharge capacity of 173.1 mAh g^− 1 between 2.8 and 4.3 V at a current density of 16 mA g^− 1 and exhibiting good cycling performance.     

Characterization of yttrium substituted LiNi0.33Mn0.33Co0.33O2 cathode material for lithium secondary cells

LiNi_0.33−xMn_0.33Co_0.33Y_xO₂ materials are synthesized by Y³⁺ substitute of Ni²⁺ to improve the cycling performance and rate capability. The influence of the Y³⁺ doping on the structure and electrochemical properties are investigated by means of X-ray diffraction (XRD), scanning electron microscope (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS) and galvanostatic charge/discharge tests. LiNi_0.33Mn_0.33Co_0.33O₂ exhibits the capacity retentions of 89.9 and 87.8% at 2.0 and 4.0 C after 40 cycles, respectively. After doping, the capacity retentions of LiNi_0.305Mn_0.33Co_0.33Y_0.025O₂ are increased to 97.2 and 95.9% at 2.0 and 4.0 C, respectively. The discharge capacity of LiNi_0.305Mn_0.33Co_0.33Y_0.025O₂ at 5.0 C remains 75.7% of the discharge capacity at 0.2 C, while that of LiNi_0.33Mn_0.33Co_0.33O₂ is only 47.5%. EIS measurement indicates that LiNi_0.305Mn_0.33Co_0.33Y_0.025O₂ electrode has the lower impedance value during cycling. It is considered that the higher capacity retention and superior rate capability of Y-doped samples can be ascribed to the reduced surface film resistance and charge transfer resistance of the electrode during cycling.     

High capacity ZnFe2O4 anode material for lithium ion batteries

A nanostructured ternary transition metal oxide, ZnFe₂O₄, is synthesized via the simple polymer pyrolysis method. The characteristics of the material are examined by thermogravimetry, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The electrochemical test results show that this method of ZnFe₂O₄ synthesis produces high specific capacities and good cycling performance, with an initial specific capacity as high as 1419.6 mAh g⁻¹ at first discharge that is maintained at over 800 mAh g⁻¹ even after 50 charge–discharge cycles. The electrode also presents a good rate capability, with a high rate of 4C (1C = 928 mA g⁻¹), a reversible specific capacity that can be as high as 400 mAh g⁻¹. ZnFe₂O₄ is a potential alternative to high-performance nanostructured anode material in lithium ion batteries.     

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.     

Hollow CuFe2O4 spheres encapsulated in carbon shells as an anode material for rechargeable lithium-ion batteries

We report here a polymer-templated hydrothermal growth method and subsequent calcination to achieve carbon coated hollow CuFe₂O₄ spheres (H–CuFe₂O₄@C). This material, when used as anode for Li-ion battery, retains a high specific capacity of 550 mAh g⁻¹ even after the 70th cycle, which is much higher than those of both CuFe₂O₄@C (∼300 mAh g⁻¹) and H–CuFe₂O₄ (∼120 mAh g⁻¹). And galvanostatic cycling at different current densities reveals that a capacity of 480 mAh g⁻¹, 91% recovery of the specific capacity cycling at 100 mA g⁻¹, can be obtained even after 50 cycles running from 100 to 1600 mA g⁻¹. The significantly enhanced electrochemical performances of H–CuFe₂O₄@C with regard to Li-ion storage are ascribed to the following factors: (1) the hollow void, which could mitigate the pulverization of electrode and facilitate the lithium-ion, electron and electrolyte transport; (2) the conductive carbon coating, which could enhance the conductivity, alleviate the agglomeration problem, prevent the formation of an overly thick SEI film and buffer the electrode. Such a structural motif of H–CuFe₂O₄@C is promising, for electrode materials of LIBs, and points out a general strategy for creating other hollow-shell electrode materials with improved electrochemical performances.     

Preparation and characterization of core–shell structure Fe3O4/C nanoparticles with unique stability and high electrochemical performance for lithium-ion battery anode material

Core–shell structure carbon coating Fe₃O₄ nanoparticles are prepared by a two-step method. The crystalline structure and the electrochemical performance of the prepared samples are investigated. The results indicate that a uniform and continuous carbon layer is formed on the surface of Fe₃O₄ nanoparticles. The core–shell structure Fe₃O₄/C nanoparticles show a high initial discharge capacity of 1546 mAh g⁻¹ and a specific stable discharge capacity of about 800 mAh g⁻¹ at 0.5 C with no noticeable capacity fading up to 100 cycles.     

A study on electrochemical characteristics of LiCoO2/LiNi1/3Mn1/3Co1/3O2 mixed cathode for Li secondary battery

In this study, the LiCoO₂/LiNi_1/3Mn_1/3Co_1/3O₂ mixed cathode electrodes were prepared and their electrochemical performances were measured in a high cut-off voltage. As the contents of LiNi_1/3Mn_1/3Co_1/3O₂ in the mixed cathode increases, the reversible specific capacity and cycleability of the electrode enhanced, but the rate capability deteriorated. On the contrary, the rate capability of the cathode enhanced but the reversible specific capacity and cycleability deteriorated, according to increasing the contents of LiCoO₂ in the mixed cathode. The cell of LiCoO₂/LiNi_1/3Mn_1/3Co_1/3O₂ (50:50, wt.%) mixed cathode delivers a discharge capacity of ca. 168 mAh/g at a 0.2 C rate. The capacity of the cell decreased with the current rate and a useful capacity of ca. 152 mAh/g was obtained at a 2.0 C rate. However, the cell shows very stable cycleability: the discharge capacity of the cell after 20th charge/discharge cycling maintains ca. 163 mAh/g.     

Preparation of LiNi1/3Co1/3Mn1/3O2/polytriphenylamine cathode composites with enhanced electrochemical performances towards reversible lithium storage

A series of LiNi_1/3Co_1/3Mn_1/3O₂/polytriphenylamine composites were successfully synthesized by ultrasound dispersion method. LiNi_1/3Co_1/3Mn_1/3O₂/polytriphenylamine (5.0?wt%) composite with small and homogeneous particle size exhibited excellent electrochemical performance, which delivered an initial discharge capacity of 223.7?mAh g^?1 with a capacity retention of 84.39% after 100 cycles in the voltage range of 2.5–4.5?V and at a current density of 0.2C. Moreover, an excellent specific discharge capacity of 127.3?mAh g^?1 at a current density 5C indicates a superior rate performance of the LiNi_1/3Co_1/3Mn_1/3O₂/polytriphenylamine (5.0?wt%) composite. The good electrochemical performances of the composite can be attributed to the introduction of polytriphenylamine, which increased electrical conductivity, decreased charge transfer resistance and increased Li⁺ ion diffusion ability. These noteworthy results demonstrated that LiNi_1/3Co_1/3Mn_1/3O₂/polytriphenylamine composites might be potential cathode materials for lithium ion batteries.     

A comparison of preparation method on the electrochemical performance of cathode material Li[Li0.2Mn0.54Ni0.13Co0.13]O2 for lithium ion battery

Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ as a cathode material for Li-ion battery has been successfully prepared by co-precipitation (CP), sol–gel (SG) and sucrose combustion (SC) methods. The prepared materials were characterized by XRD, SEM, BET and electrochemical measurements. The XRD result shows that the Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ materials prepared by different methods all form a pure phase with good crystallinity. SEM images and BET data present that the SC-material exhibited the smallest particle size (ca. 0.1 μm) and the highest surface area (7.4635 m² g⁻¹). The tap density of SC-material is lower than that of CP- and SG-materials. The result of rate performance tests indicates that the SC-material showed the best rate capability with the highest discharge capacity of 178 mAh g⁻¹ at 5.0 C, followed by SG-material and then CP-material. However, the cycling stability of SC-material tested at 0.1 and 0.5 C is relatively poor as compared to that of SG-material and CP-material. The result of EIS measurements reveals that large surface area and small particle size of the SC-electrode result in more SEI layer formation because of the increased side reactions with the electrolyte during cycling, which deteriorates the electrode/electrolyte interface and thus leads to the faster capacity fading of the SC-material.     

Effect of ZnO modification on the performance of LiNi0.5Co0.25Mn0.25O2 cathode material

ZnO was coated on LiNi_0.5Co_0.25Mn_0.25O₂ cathode (positive electrode) material for lithium ion battery via sol–gel method to improve the performance of LiNi_0.5Co_0.25Mn_0.25O₂. The X-ray diffraction (XRD) results indicated that the lattice structure of LiNi_0.5Co_0.25Mn_0.25O₂ was not changed distinctly after surface coating and part of Zn²⁺ might dope into the lattice of the material. Energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) proved that ZnO existed on the surface of LiNi_0.5Co_0.25Mn_0.25O₂. Charge and discharge tests showed that the cycle performance and rate capability were improved by ZnO coating, however, the initial capacity decreased dramatically with increasing the amount of ZnO. Differential scanning calorimetry (DSC) results showed that thermal stability of the materials was improved. The XPS spectra after charge–discharge cycles showed that ZnO coated on LiNi_0.5Co_0.25Mn_0.25O₂ promoted the decomposition of the electrolyte at the early stage of charge–discharge cycle to form more stable SEI layer, and it also can scavenge the free acidic HF species from the electrolyte. The electrochemical impedance spectroscopy (EIS) results showed ZnO coating could suppress the augment of charge transfer resistance upon cycling.     

WO3 membrane-encapsulated layered LiNi0.6Co0.2Mn0.2O2 cathode material for advanced Li-ion batteries

Despite Nickel-rich materials have all the advantages of high capacity, long cycle life and low cost, there is still a disadvantage that the capacity decreases rapidly as the number of cycles increases. In order to solve this problem, WO₃ was uniformly coated on the surface of LiNi_0.6Co_0.2Mn_0.2O₂ cathode materials by wet coating, and its cycling performance was greatly improved with the higher capacity. The coated materials were analyzed by X-ray diffraction(XRD), Scanning electron microscope (SEM), high resolution Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy(XPS). The results showed that the coating thickness was around 3.15?nm, and some tungsten ions were doped into the lattice of the near surface area of the LiNi_0.6Co_0.2Mn_0.2O₂ material. In addition, the results of charge-discharge test showed that 1?wt%WO₃ coating LiNi_0.6Co_0.2Mn_0.2O₂ had the best performance, and delivered a discharge capacity of 140 mAh g^?1 (the capacity retention rate is 84.8%) in the potential interval of 2.8–4.3?V at 1?C (1?C?=?165?mA?g^?1) after 200 cycles, while the bare cathode material only delivered a discharge capacity of 120 mAhg^?1 (the capacity retention rate is 75%). The phenomenon indicates that the WO₃ coating plays a role in inhibiting the harmful side reactions between the cathode material and the electrolyte, improving the electrochemical and structure stability of LiNi_0.6Co_0.2Mn_0.2O₂ cathode materials.     

A novel method for preparation of macroposous lithium nickel manganese oxygen as cathode material for lithium ion batteries

A simple one-step route using gas template method is applied to synthesize macroporous LiNi_0.5Mn_0.5O₂ which is characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer–Emmett–Telle (BET) surface area, charge–discharge tests and electrochemical impedance spectroscopy (EIS) measurements. The as-synthesized material shows pure crystalline phase of LiNi_0.5Mn_0.5O₂, while the microstructure is comprised of macrospores ranging from 0.2 to 0.5 μm. The first discharge capacity is of 174 mAh g⁻¹ at 0.1 C rate, which is much higher than that of the material synthesized by the conventional solid state reaction method. Furthermore, the macroporous LiNi_0.5Mn_0.5O₂ material shows remarkable rate capacity and cycle stability, which may be attributed to the shorter lithium ion diffusion distance and better electrolyte penetration.     

Electrochemical properties of nano- and micro-sized LiNi0.5Mn1.5O4 synthesized via thermal decomposition of a ternary eutectic Li-Ni-Mn acetate

Nano- and micro-sized LiNi_0.5Mn_1.5O₄ particles are prepared via the thermal decomposition of a ternary eutectic Li-Ni-Mn acetate. Lithium acetate, nickel acetate and manganese acetate can form a ternary eutectic Li-Ni-Mn acetate below 80 °C. After further calcination, nano-sized LiNi_0.5Mn_1.5O₄ particles can be obtained at an extremely low temperature (500 °C). When the sintering temperature goes above 700 °C, the particle size increases, and at 900 °C micro-sized LiNi_0.5Mn_1.5O₄ particles (with a diameter of about 4 μm) are obtained. Electrochemical tests show that the micro-sized LiNi_0.5Mn_1.5O₄ powders (sintered at 900 °C) exhibit the best capacity retention at 25 °C, and after 100 cycles, 97% of initial discharge capacity can still be reached. Nano-sized LiNi_0.5Mn_1.5O₄ powders (sintered at 700 °C) perform the best at low temperatures; when cycled at −10 °C and charged and discharged at a rate of 1 C, nano-sized LiNi_0.5Mn_1.5O₄ powders can deliver a capacity as high as 110 mAh g⁻¹.     

Synthesis of LiNi1/3Co1/3Mn1/3O2 cathode materials by using a supercritical water method in a batch reactor

LiNi_1/3Co_1/3Mn_1/3O₂ and LiCoO₂ cathode materials were synthesized by using a supercritical water (SCW) method with a metal salt solution in a batch reactor. Stoichiometric LiNi_1/3Co_1/3Mn_1/3O₂ was successfully synthesized in a 10-min reaction without calcination, while overlithiated LiCoO₂ (Li_1.15CoO₂) was synthesized using the batch SCW method. The physical properties and electrochemical performances of LiNi_1/3Co_1/3Mn_1/3O₂ were compared to those of Li_1.15CoO₂ by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), and charge/discharge cycling tests. The XRD pattern of LiNi_1/3Co_1/3Mn_1/3O₂ was found to be similar to that of Li_1.15CoO₂, showing clear splitting of the (0 0 6)/(1 0 2) and (1 0 8)/(1 1 0) peak pairs as particular characteristics of the layered structure. In addition, both cathode powders showed good crystallinity and phase purity, even though a short reaction time without calcination was applied to the SCW method. The initial specific discharge capacities of the Li_1.15CoO₂ and LiNi_1/3Co_1/3Mn_1/3O₂ powders at a current density of 0.24 mA/cm² in 2.5-4.5 V were 149 and 180 mAh/g, and their irreversible capacity loss was 20 and 17 mAh/g, respectively. The discharge capacities of the Li_1.15CoO₂ and LiNi_1/3Co_1/3Mn_1/3O₂ powders decreased with cycling and remained at 108 and 154 mAh/g after 30 cycles, which are 79% and 89% of the initial capacities. Compared to the overlithiated LiCoO₂ cathode powders, the LiNi_1/3Co_1/3Mn_1/3O₂ cathode powders synthesized by SCW method had better electrochemical performances.     

Surface structural change of ZnO-coated LiNi0.5Mn1.5O4 spinel as 5 V cathode materials at elevated temperatures

LiNi_0.5Mn_1.5O₄ powder was synthesized via sol-gel method and coated with ZnO in order to test the electrochemical cyclability of the material as a cathode for the secondary Li battery in the 5 V range at 55 °C. The ZnO-coated LiNi_0.5Mn_1.5O₄ powder nearly maintained its initial capacity of 137 mA h g⁻¹ after 50 cycles whereas the uncoated powder was able to retain no more than 10% of the initial capacity after 30 cycles. TEM analysis of the cycled cathodes suggests that the formation of the graphitic surface phase, hindering the Li migration, may be responsible for the rapid capacity loss of the uncoated material while no such phase was observed on the surface of the ZnO coated LiNi_0.5Mn_1.5O₄ powder.