Synthesis of LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> nanoparticles by modified Pechini method and their enhanced rate capability

Layered LiNi_1/3Co_1/3Mn_1/3O₂ nanoparticles were prepared by modified Pechini method and used as cathode materials for Li-ion batteries. The pyrolytic behaviors of the foamed precursors were analyzed by use of simultaneous thermogravimetric and differential thermal analysis (TG-DTA). Structure, morphology and electrochemical performance characterization of the samples were investigated by X-ray diffraction (XRD), field emission scanning electron macroscopy(SEM), Brunauer-Emmett-Teller (BET) specific surface area and charge–discharge tests. The results showed that the samples prepared by modified Pechini method caclined at 900 °C for 10 h were indexed to pure LiNi_1/3Co_1/3Mn_1/3O₂ with well hexagonal structure. The particle size was in a range of 100–300 nm. The specific surface area was larger than that of the as-obtained sample by Pechini method. Initial discharge capacity of 163.8 mAh/g in the range 2.8–4.4 V (vs. Li/Li⁺) and at 0.1C for LiNi_1/3Co_1/3Mn_1/3O₂ prepared by modified Pechini method was obtained, higher than that of the sample prepared by Pechini method (143.5 mAh/g). Moreover, the comparison of electrochemical results at different current rates indicated that the sample prepared by modified Pechini method exhibited improved rate capability.     

Effect of lithium boron oxide glass coating on the electrochemical performance of LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript>

The effect of the lithium boron oxide glass coating on the electrochemical performance of LiNi_1/3Co_1/3Mn_1/3O₂ has been investigated via solution method. The morphology, structure, and electrochemical properties of the bare and coated LiNi_1/3Co_1/3Mn_1/3O₂ are characterized by scanning electron microscopy, X-ray diffraction, electrochemical impedance spectroscopy, and charge–discharge tests. The results showed that the lattice structure of LiNi_1/3Co_1/3Mn_1/3O₂ is not changed after coating. The coating sample shows good high-rate discharge performance (148 mAh g⁻¹ at 5.0 C rate) and cycling stability even at high temperature (with the capacities retention about 99% and 87% at room and elevated temperature after 50 cycles). The Li⁺ diffusion coefficient is also largely improved, while the charge transfer resistance, side reactions within cell, and the erosion of Hydrofluoric Acid all reduced. Consequently, the good electrochemical performances are obtained.     

Al,B, and F doped LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> as cathode material of lithium-ion batteries

A series of the mixed transition metal compounds, Li[(Ni_1/3Co_1/3Mn_1/3)_1–x-y Al _x B _y ]O_2-z F _z (x = 0, 0.02, y = 0, 0.02, z = 0, 0.02), were synthesized via coprecipitation followed by a high-temperature heat-treatment. XRD patterns revealed that this material has a typical α-NaFeO₂ type layered structure with R3^- m space group. Rietveld refinement explained that cation mixing within the Li(Ni_1/3Co_1/3Mn_1/3)O₂ could be absolutely diminished by Al-doping. Al, B and F doped compounds showed both improved physical and electrochemical properties, high tap-density, and delivered a reversible capacity of 190 mAh/g with excellent capacity retention even when the electrodes were cycled between 3.0 and 4.7 V.     

Influence of ZnO coating on the structure,morphology and electrochemical performances for LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> material

In this paper, ZnO was applied to modify the surface of LiNi_1/3Co_1/3Mn_1/3O₂ cathode material by a simple method. Powder X-ray diffraction (XRD) results show that both of the pristine material and the modified material were well crystallized and closely similar to each other. The crystal parameters of pristine material increased by modified measure. Scan electron microscope (SEM) pictures exhibit that the quasispherical pristine material was modified to the squareness one. Transmission electron microscope (TEM) image clearly elucidates that ZnO (several nanometers to 20 nm) was successful coated on surface of LiNi_1/3Co_1/3Mn_1/3O₂. X-ray photo-electron spectrometry (XPS) is used to characterize the composite of the coating layer on the surface of modified material. Electrochemical performance results present that the ZnO coating layer decrease the initial capacities of LiNi_1/3Co_1/3Mn_1/3O₂ by increasing the surface layer resistances. However, the cycling performance of LiNi_1/3Co_1/3Mn_1/3O₂ was effectively improved by the ZnO coating layer.     

Electrochemical properties of nano-crystalline LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> synthesized by polymer-pyrolysis method

LiNi_0.5Mn_1.5O₄ powders were prepared through polymer-pyrolysis method. XRD and TEM analysis indicated that the pure spinel structure was formed at around 450 °C due to the very homogeneous intermixing of cations at the atomic scale in the starting precursor in this method, while the well-defined octahedral crystals appeared at a relatively high calcination temperature of 900 °C with a uniform particle size of about 100 nm. When cycled between 3.5 and 4.9 V at a current density of 50 mA/g, the as prepared LiNi_0.5Mn_1.5O₄ delivered an initial discharge capacity of 112.9 mAh/g and demonstrated an excellent cyclability with 97.3% capacity retentive after 50 cycles.     

Effects of Mg,Al Co-doping into Mn site on electrochemical performance of LiNi<Subscript>0.5</Subscript>Co<Subscript>0.2</Subscript>Mn<Subscript>0.3</Subscript>O<Subscript>2</Subscript>

In order to study the influence of multiple ions doping into single-site on the structure and electrochemical properties of Ni-rich layered-structure cathode material LiNi_0.5Co_0.2Mn_0.3O₂, the coprecipitation of hydroxides was applied to synthesize Mg, Al co-doped cathode material LiNi_0.5Co_0.2Mn_0.3–x Mg_1/2x Al_1/2x O₂ (x = 0.00, 0.01, 0.02, 0.04) in this paper. Morphology and structure, kinetic parameter, impedance and electrochemical performance of the material were respectively characterized by SEM, XRD, CV, EIS and galvanostatic charge/discharge test. The results of comprehensive analysis showed that the properties of material were improved obviously when the amount of doping was 0.02. At this amount of doping, the corresponding material has smaller cation mixing, higher hexagonal ordering of layered-structure, larger Li⁺ ion diffusion coefficients which are 2.444 × 10^–10 and 4.186 × 10^–10 cm² s^–1 for Li+ intercalation and deintercalation respectively, smaller impedance which is 33.93 Ω, higher specific capacity of first-discharge which is 168.01 mA h g^–1 and higher capacity retention rate which is up to 95.06% after 20 cycles at 0.5 C (100 mA g^–1).     

Electrochemical dissolution of Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> in acid solutions

The present study deals with the electrochemical reductive dissolution of Mn₃O₄, which was added to carbon-paste electroactive electrodes (CPEEs) in acid solutions. It was found that in the experimental conditions the thermodynamically stable form of manganese was . Kinetic features of the electrochemical reductive dissolution of Mn₃O₄, which was realized under potential cycling conditions (+1.0 V→−0.7 V→+1.0 V), were determined by the electrode polarization direction. It was shown that the cathodic reduction of Mn₃O₄ was accomplished in three stages. Manganese was dissolved in the supporting solution only at the third stage. The first two stages involved solid-phase reactions. The anodic cycling stage included an active dissolution of Mn₃O₄ and the lower manganese oxide (MnO) accumulated on the electrode surface during the cathodic reduction.     

Electrochemical dissolution of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> in acidic solutions

The cyclic voltammetry method was used to study the regularities of the electrochemical behavior of cobalt cobaltite in an acidic medium. It is shown that cathodic reduction of Co₃O₄ in the studied range of potentials of +1.0 to −0.8 V is a multistage process occurring according to the scheme:      

Effect of the preparation method of the cathode material LiNi<Subscript>0.33</Subscript>Mn<Subscript>0.33</Subscript>Co<Subscript>0.33</Subscript>O<Subscript>2</Subscript> on the electrochemical characteristics of a lithium ion cell

Complex metal oxides with the composition LiNi_0.33Mn_0.33Co_0.33O₂ prepared by various methods: sol–gel method, solid-phase method, and thermal destruction of metal-containing compounds in oil were studied. The results of elemental analysis, TGA/DSC, powder X-ray diffraction, SEM, TEM, as well as the results of electrochemical testing of the cathodes based on the obtained materials are presented. The complex metal oxides LiNi_0.33Mn_0.33Co_0.33O₂ prepared by sol–gel processes and thermal destruction of metal-containing compounds in oil consist of primary nanosized crystallites with an average size of 90 nm covered by a nanometer carbon layer, which improves the electrochemical characteristics of lithium ion batteries.     

Towards high-performance cathode materials for lithium-ion batteries: Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-coated LiNi<Subscript>0.8</Subscript>Co<Subscript>0.15</Subscript>Zn<Subscript>0.05</Subscript>O<Subscript>2</Subscript>

Zn-doped LiNi_0.8Co_0.2O₂ exhibits impressive electrochemical performance but suffers limited cycling stability due to the relative large size of irregular and bare particle which is prepared by conventional solid-state method usually requiring high calcination temperature and prolonged calcination time. Here, submicron LiNi_0.8Co_0.15Zn_0.05O₂ as cathode material for lithium-ion batteries is synthesized by a facile sol-gel method, which followed by coating Al₂O₃ layer of about 15 nm to enhance its electrochemistry performance. The as-prepared Al₂O₃-coated LiNi_0.8Co_0.15Zn_0.05O₂ cathode delivers a highly reversible capacity of 182 mA h g^?1 and 94% capacity retention after 100 cycles at a current rate of 0.5 C, which is much superior to that of bare LiNi_0.8Co_0.15Zn_0.05O₂ cathode. The enhanced electrochemistry performance can be attributed to the Al₂O₃-coated protective layer, which prevents the direct contact between the LiNi_0.8Co_0.15Zn_0.05O₂ and electrolyte. The escalating trend of Li-ion diffusion coefficient estimated form electrochemical impedance spectroscopic (EIS) also indicate the enhanced structural stability of Al₂O₃-coated LiNi_0.8Co_0.15Zn_0.05O₂, which rationally illuminates the protection mechanism of the Al₂O₃-coated layer.     

Influence of Li source on tap density and high rate cycling performance of spherical Li[Ni<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>]O<Subscript>2</Subscript> for advanced lithium-ion batteries

Spherical Li[Ni_1/3Co_1/3Mn_1/3]O₂ cathode materials with different microstructure have been prepared by a continuous carbonate co-precipitation method using LiOH⋅H₂O, Li₂CO₃, CH₃COOLi⋅2H₂O and LiNO₃ as lithium source. The effects of Li source on the physical and electrochemical properties of Li[Ni_1/3Co_1/3Mn_1/3]O₂ are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical measurements. The results show that the morphology, tap density and high rate cycling performance of Li[Ni_1/3Co_1/3Mn_1/3]O₂ spherical particles are strongly affected by Li source. Among the four Li sources used in this study, LiOH⋅H₂O is beneficial to enhance the tap density of Li[Ni_1/3Co_1/3Mn_1/3]O₂, and the tap density of as-prepared sample reaches 2.32 g cm⁻³. Meanwhile, Li₂CO₃ is preferable when preparing the Li[Ni_1/3Co_1/3Mn_1/3]O₂ with high rate cycling performance, upon extended cycling at 1 and 5C rates, 97.5% and 92% of the initial discharge capacity can be maintained after 100 cycles.     

Rational design of double-confined Mn<Subscript>2</Subscript>O<Subscript>3</Subscript>/S@Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocube cathodes for lithium-sulfur batteries

Due to the high specific capacities and environmental benignity, lithium-sulfur (Li-S) batteries have shown fascinating potential to replace the currently dominant Li-ion batteries to power portable electronics and electric vehicles. However, the shuttling effect caused by the dissolution of polysulfides seriously degrades their electrochemical performance. In this paper, Mn₂O₃ microcubes are fabricated to serve as the sulfur host, on top of which Al₂O₃ layers of 2 nm in thickness are deposited via atomic layer deposition (ALD) to form Mn₂O₃/S (MOS) @Al₂O₃ composite electrodes. The MOS@Al₂O₃ electrode delivers an excellent initial capacity of 1012.1 mAh g^?1 and a capacity retention of 78.6% after 200 cycles at 0.5 C, and its coulombic efficiency reaches nearly 99%, giving rise to much better performance than the neat MOS electrode. These findings demonstrate the double confinement effect of the composite electrode in that both the porous Mn₂O₃ structure and the atomic Al₂O₃ layer serve as the spacious host and the protection layer of sulfur active materials, respectively, for significantly improved electrochemical performance of the Li-S battery.     

Understanding the accumulated cycle capacity fade caused by the secondary particle fracture of LiNi<Subscript>1-x-y</Subscript>Co<Subscript>x</Subscript>Mn<Subscript>y</Subscript>O<Subscript>2</Subscript> cathode for lithium ion batteries

Effect of secondary particle fracture on the accumulated cycle capacity fade of LiNi_1-x-yCo_xMn_yO₂ cathode is difficult to evaluate since performance degradation of electrode material is always caused by several factors simultaneously. Herein, LiNi_0.5Co_0.2Mn_0.3O₂ single particles (Sin-P) are prepared and introduced as a reference to understand the accumulated cycle capacity fade caused by the secondary particle fracture of LiNi_0.5Co_0.2Mn_0.3O₂ secondary particles (Sec-P). Sec-P exhibited accumulated cycle capacity fade compared to Sin-P when cycled at high rate, high voltage, and high temperature. The accumulated cycle capacity fade was mainly caused by the secondary particle fracture of Sec-P, which was confirmed by the X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscope (SEM) analysis. Further, XPS and electrochemical impedance spectroscopy (EIS) analysis indicated that the surface property changes and resistance rise were responsible for the accumulated cycle capacity fade. The study provides a novel way to analyze the accumulated cycle capacity fade caused by the secondary particle fracture and is helpful for understanding the performance degradation mechanism of electrode material.     

2-pyrrolidone - capped Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> nanocrystals

Water-soluble Mn₃O₄ nanocrystals have been prepared through thermal decomposition in a high temperature boiling solvent, 2-pyrrolidone. The final product was characterized with XRD, SEM, TEM, FTIR and Zeta Potential measurements. Average crystallite size was calculated as ∼15 nm using XRD peak broadening. TEM analysis revealed spherical nanoparticles with an average diameter of 14±0.4 nm. FTIR analysis indicated that 2-pyrrolidone coordinates with the Mn₃O₄ nanocrystals only via O from the carbonyl group, thus confining their growth and protecting their surfaces from interaction with neighboring particles.      

Improvement of the electrochemical properties of a LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> cathode material formed by a new solid-state synthesis method

In order to avoid the shortcomings of large particle size and poor uniformity of material synthesized by the traditional solid-state method, this paper utilizes a simple improvement of calcination process (i.e., calcination–milling–recalcination) based on the traditional solid-state synthesis to successfully prepare a large number of well-distributed, micrometer-sized, spherical secondary LiNi_0.5Mn_1.5O₄ particles. Each particle is composed of nano- and/or sub-micrometer-sized grains. Results of the electrochemical performance tests show that the material exhibits a remarkable cycle performance and rate capability compared with that obtained from traditional synthesis method; the spherical LiNi_0.5Mn_1.5O₄ particles can deliver a large capacity of 135.8 mAh g^?1 at a 1 C discharge rate with a high retention of 77 % after 741 cycles and a good capacity of 105.9 mAh g^?1 at 10 C. Cyclic voltammetry measurements confirm that the significantly improved electrochemical properties are due to enhanced electronic conductivity and lithium-ion diffusion coefficient resulting from the optimized morphology and particle size. This improved method is more suitable for mass production.     

Promoted porous Co<Subscript>3</Subscript>O<Subscript>4</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts for ammonia decomposition

Transition metal catalysts have been considerably used for NH₃ decomposition because of the potential application in CO_x-free H₂ generation for fuel cells. However, most transition metal catalysts prepared via traditional synthetic approaches performed the inferior stability due to the agglomeration of active components. Here, we adopted an efficient method, aerosol-assisted self-assembly approach (AASA), to prepare the optimized cobalt-alumina (Co₃O₄-Al₂O₃) catalysts. The Co₃O₄-Al₂O₃ catalysts exhibited excellent catalytic performance in the NH3 decomposition reaction, which can reach 100% conversion at 600 °C and maintain stable for 72 h at a gaseous hourly space velocity (GHSV) of 18000 cm³ g_cat^?1 h^?1. The catalysts were characterized by various techniques including transmission electron microscope (TEM), scanning electron microscope (SEM), nitrogen sorption, temperature-programmed reduction by hydrogen (H₂-TPR), ex-situ/in-situ Raman and ex-situ/in-situ X-ray diffraction (XRD) to obtain the information about the structure and property of the catalysts. H₂-TPR and in-situ XRD results show that there is strong interaction between the cobalt and alumina species, which influences the redox properties of the catalysts. It is found that even a low content of alumina (10 at%) is able to stabilize the catalysts due to the adequate dispersion and rational interaction between different components, which ensures the high activity and superior stability of the cobalt-alumina catalysts.     

Glycine-assisted combustion synthesis and electrochemical behavior of LiNi<Subscript>0.5</Subscript>Mn<Subscript>0.5</Subscript>O<Subscript>2</Subscript> nanoparticles under microwave irradiation

Layered LiNi_0.5Mn_0.5O₂ nanoparticles have been successfully prepared by the glycine-assisted combustion method under microwave irradiation. The exothermic reaction can generate a large quantity of heat rapidly leading to the formation and crystallization of LiNi_0.5Mn_0.5O₂. From the X-ray diffraction and scanning electronic microscopy results, the resulting powders have a well-developed layered structure and average particle-size is about 80 nm. The chemical composition analysis and electrochemical characteristics of the obtained LiNi_0.5Mn_0.5O₂ nanoparticles as cathode material for rechargeable lithium-ion battery were also investigated. The improved electrochemical performances of the layered LiNi_0.5Mn_0.5O₂ nanoparticles might be ascribed to the nanostructure of the powders and the unique combustion synthesis under microwave irradiation.     

Effects of Nb substitution on structure and electrochemical properties of LiNi<Subscript>0.7</Subscript>Mn<Subscript>0.3</Subscript>O<Subscript>2</Subscript> cathode materials

Nb-doped cathode materials with the formula Li(Ni_0.7Mn_0.3)_1?xNb_xO₂ (x?=?0, 0.01, 0.02, 0.03, 0.04) have been prepared successfully by calcining the mixtures of LiOH·H₂O, Nb₂O₅, and Ni_0.7Mn_0.3(OH)₂ precursor formed through a simple continuous co-precipitation method. The effects of Nb substitution on the crystal structure and electrochemical properties of LiNi_0.7Mn_0.3O₂ were studied systematically by X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), and various electrochemical measurements. The results show that the lattice parameters of the Nb substitution LiNi_0.7Mn_0.3O₂ samples are slightly larger than that of pure LiNi_0.7Mn_0.3O₂, and the basic α-NaFeO₂ layered structure does not change with the Nb doping. What’s more, better morphology, lower resistance, and good cycle stability were obtained after Nb substitution. In addition, CV test exhibits that Nb doping results in lower electrode polarization and XPS results indicate that the valence of Mn kept constant but the component of Ni³⁺ decreased after doping. All the results indicate that Nb doping in LiNi_0.7Mn_0.3O₂ is a promising method to improve the properties of Ni-rich lithium-ion batteries positive-electrode materials.     

Effects of polyvinyl alcohol on the electrochemical performance of LiNi<Subscript>0.8</Subscript>Co<Subscript>0.15</Subscript>Al<Subscript>0.05</Subscript>O<Subscript>2</Subscript> cathode material

In view of the close relationship between the morphology of LiNi_0.8Co_0.15Al_0.05O₂ (NCA) and its electrochemical performance, polyvinyl alcohol (PVA) was added to control the NCA morphology. And thus a new NCA cathode material modified by PVA (NCA-PVA) was prepared. The morphology and structure of the obtained samples were characterized by X-ray diffraction, scanning electron microscopy, and laser diffraction. The electrochemical performance was characterized with electrochemical workstation and cell tester by assembling into CR2032 coin-type half-cell. The results show that the obtained NCA-PVA has a better layer structure and smaller cation mixing degree, smaller particle size, and more uniform particle size distribution than the pristine NCA without adding PVA. The electrochemical performance is also improved: the initial discharge capacity increases from 143.36 to 184.84 mAh g^?1. And the charge-discharge efficiency increases from 78.25 to 86.42%. The specific discharge capacities of NCA-PVA are all higher than that of the NCA (about 50 mAh g^?1) at all testing rates (0.1, 0.2, 0.5, 1.0, 2.0, and 5.0 C).     

Synthesis and electrochemical properties of Ca-doped LiNi<Subscript>0.8</Subscript>Co<Subscript>0.2</Subscript>O<Subscript>2</Subscript> cathode material for lithium ion battery

LiNi_0.8Co_0.2O₂ and Ca-doped LiNi_0.8Co_0.2O₂ cathode materials have been synthesized via a rheological phase reaction method. X-ray diffraction studies show that the Ca-doped material, and also the discharged electrode, maintains a hexagonal structure even when cycled in the range of 3.0–4.35 V (vs Li⁺/Li) after 100 cycles. Electrochemical tests show that Ca doping significantly improves the reversible capacity and cyclability. The improvement is attributed to the formation of defects caused by the partial occupancy of Ca²⁺ ions in lithium lattice sites, which reduce the resistance and thus improve the electrochemical properties.