The characteristics of Li(CoxNi1 − x)O2 cathode powders formed from the fine-sized Co3O4/NiO precursor powders

Li(Co_xNi_1 − x)O₂ (0 ≤ x ≤ 1) cathode powders were prepared by solid state reaction method using Co₃O₄/NiO precursor powders obtained by spray pyrolysis. The effect of the ratios of cobalt and nickel components on the characteristics of Co₃O₄/NiO precursor and Li(Co_xNi_1 − x)O₂ cathode powders were investigated. The Co₃O₄/NiO precursor powders with the ratios of cobalt and nickel components as 1/0, 0.75/0.25 and 0.5/0.5 had submicron size and regular morphologies. On the other hand, the Co₃O₄/NiO powders with the high contents of nickel component had aggregated morphologies of submicron size primary powders. The fine-sized precursor powders formed the fine-sized LiCoO₂ and Li(Co_0.75Ni_0.25)O₂ cathode powders by solid state reaction with LiOH powders. However, the high contents of the nickel component of the Co₃O₄/NiO precursor powders formed the Li(Co_xNi_1 − x)O₂ (0 ≤ x ≤ 0.5) cathode powders with aggregated morphologies and large sizes. The discharge capacities of the powders increased with increasing the nickel content into the Li(Co_xNi_1 − x)O₂ cathode powders up to 188 mAh/g.     

Nanosize cobalt oxides as anode materials for lithium-ion batteries

Nanosize cobalt oxides (Co₃O₄) were synthesised by chemical decomposition of cobalt octacarbonyl in toluene at low temperature. Electrochemical properties of as-prepared Co₃O₄ as anodes in Li-ion cells were tested. The nanosized Co₃O₄ electrode demonstrate a stable reversible lithium storage capacity of 360 mAh/g within 30 cycles. The reactivity of as-prepared Co₃O₄ in Li-ion cells could be attributed to nanosize particles of Co₃O₄ and its lithiation products.     

Structure and electrochemical properties of Li(Ni0.5Mn0.5)1-xTixO2 prepared by one-step solid state reaction

The layered compound Li(Ni_0.5Mn_0.5)_1-xTi_xO₂ powders were prepared with Ni(OH)₂, MnCO₃, Li₂CO₃ and TiO₂ by one-step solid state reaction. The effect of doping Ti on the structure and electrochemical properties was studied. The XRD results indicate that the powders with 0≤x≤0.05 have good layered structure and trace of impurity appears in the samples with x≥0.1. The SEM photographs show that the particle size distributes homogeneously and the sample with x=0.15 has larger particle size than other samples. The charge-discharge tests show that Li(Ni_0.5Mn_0.5)_0.95Ti_0.05O₂ synthesized at 800 °C for 36 h exhibits good electrochemical properties. It firstly delivers 173 mA·h/g and maintains 90% of the initial discharge capacity after 30 cycles. The cyclic voltammetry and differential capacity vs voltage curves show that the major oxidation and reduction peaks are around 3.95 V and 3.75 V, respectively, assigned to Ni²⁺/Ni⁴⁺ oxidation-reduction process. A weak peak around 4.5 V is found during the oxidation process in the first cycle, which can be regarded as the main reason of the large drop of discharge capacity in the initial cycle.     

Ternary Metal–Organic Framework Derived 2D Fe2O3/Co3O4/NiO/NC Heterostructured Nanosheets for Super Lithium Storage

Fe ₂ O ₃ /Co ₃ O ₄ /Ni O/NC nanosheets have been successfully prepared via a two-step annealing process of ternary metal coordination polymer. Attributing to the synergistic e? ects of the multiple metal oxides and the unique 2D nanosheet structure, the improved electrical conductivity and e? ective electron/ion transfer enables Fe ₂ O ₃ /Co ₃ O ₄ /Ni O/NC electrode to exhibit excellent electrochemical prope...     

Electrochemical performance of SrF2-coated LiMn2O4 cathode material for Li-ion batteries

SrF2-coated LiMn2O4 powders with excellent electrochemical performance were synthesized. The electrochemical performance of SrF2-coated LiMn2O4 electrodes was studied as function of the level of SrF2 coating. With increasing the amount of the coated-SrF2 to 2.0% （molar fraction）, the discharge capacity of LiMn2O4 decreases slightly, but the cycleability of LiMn2O4 at elevated temperature is improved obviously. In view of discharge capacity and cycleability, the 2.0% （molar fraction） coated sample shows optimum cathodic behaviors. When being cycled at 55 ℃, as-repared LiMn2O4 remains only 79% of its initial capacity after 20 cycles, whereas the 2.0% （molar fraction） coated sample shows initial discharge capacity of 108 mA-h/g, and 97% initial capacity retention.     

Effect of calcination temperature on characteristics of LiNi1/3Co1/3Mn1/3O2 cathode for lithium ion batteries

LiNi1/3Co1/3Mn1/3O2 was synthesized by sol-gel method and effect of calcination temperature on characteristics of LiNi1/3Co1/3Mn1/3O2 cathode was investigated. The structure and characteristics of LiNi1/3Co1/3Mn1/3O2 were determined by XRD, SEM and electrochemical measurements. The results show that the compound LiNi1/3Co1/3Mn1/3O2 has layered structure with hexagonal lattice. With the increase of calcination temperature, the basicity of the material decreases, and the size of primary particle rises. The LiNi1/3Co1/3Mn1/3O2 calcined at 900 ℃ for 12 h shows excellent electrochemical performances with large reversible specific capacity of 157.5 mA-h/g in the voltage range of 2.75-4.30 V and good capacity retention of 94.03% after 20 charge/discharge cycles. Capacity of LiNi1/3Co1/3Mn1/3O2 increases with enhancement of charge voltage limit, and specific discharge capacities of 179.4 mA.h/g, 203.1 mA.h/g are observed when the charge voltages limit are fixed at 4.50 V and 4.70 V, respectively.     

LiMn2O4 thin films derived by rapid thermal annealing and their performance as cathode materials for Li ion battery

1. Introduction Thin-film lithium-ion batteries have received considerable attention [1-4] because of their many possible applications, such as smart cards, CMOS-based integrated circuits, and microdevices [5-7]. Among the several thin films that can be used as cathode material for thin-film lithium-ion batter- ies, LiMn2O4 is one of the most studied cathode ma- terials [8-9] because of its relatively high-voltage plateau, nontoxicity, and good rechargeability. LiMn2O4 thin films have been…     

Synthesis and characterization of CoFe2O4 magnetic particles prepared by co-precipitation method: Effect of mixture procedures of initial solution

CoFe₂O₄ magnetic particles were prepared by co-precipitation method in 60 °C homogeneous aqueous solution without any subsequent heat treatment. It was found that the mixing procedure and Fe²⁺/Fe³⁺ ratio of initial solution were critical in the preparation of CoFe₂O₄ particles in particle size, magnetization characters, uniformity in particle size and even cation distribution in spinel structure. Two different procedures were used to precipitate CoFe₂O₄ magnetic particles. Evidenced by XRD, Mossbauer analyses and magnetization determination, particles in comparative uniformity average size were obtained in procedure A, denoted as normal pH regulation procedure, in which NaOH solution was dropped into the mixture solution of iron ions, and with the decreasing in Fe²⁺/Fe³⁺ ratio of initial solution, the particle size decreased, which followed the same rule of diversification in saturation magnetization. Uniformity in particle size lowered when procedure B, referred to as reverse pH regulation procedure, where ferrous and cobalt ions were dropped into alkaline solution, was used to precipitate CoFe₂O₄. In both procedures, with the decreasing in Fe²⁺/Fe³⁺ ratio of initial solution, the saturation magnetization decreased, while the magnetic coercivity decreased but increased sharply when Fe²⁺/Fe³⁺ ratio of initial solution was 0.     

Properties of exchange biased Co/Co3O4 bilayer films

Co/Co₃O₄ bilayer films were fabricated by RF sputtering with Co and Co₃O₄ targets. Exchange bias effect in the bilayer films was observed at 80 K by vibrating sample magnetometer. The bias effect disappeared about 240 K slightly lower than the Néel point of CoO and much higher than the Néel temperature of Co₃O₄ about 40 K. To clarify the origin of the exchange bias effect, Auger and X-ray photoelectron spectroscopy were employed and CoO was found at a transition region from Co₃O₄ layer to Co layer due to oxygen diffusion during sputtering. The angular dependence of exchange bias field H_E was obtained to obey function of H_E(θ)=18.06 (kA/m)[−cos θ+0.22 cos 3θ+0.03 cos 5θ−0.01 cos 7θ+].     

Synthesis of Co_3O_4 Nanoparticles Wrapped Within Full Carbon Matrix as an Anode Material for Lithium Ion Batteries

A facile polyol-assisted pyro-synthesis method was used to synthesize Co_3O_4 nanoparticles embedded into carbon matrix without using any conventional carbon source. The surface analysis by scanning electron microscopy showed that the Co_3O_4 nanoparticles(~20 ± 5 nm) are tightly enwrapped within the carbon matrix. CHN analysis determined the carbon content was only 0.11% in the final annealed sample. The Co_3O_4@carbon exhibited high capacities and excellent cycling performance as an anode at various current rates(such as 914.4 and 515.5 mAh g~(-1) at 0.25 and1.0 C, respectively, after 50 cycles; 318.2 mAh g~(-1) at a high current rate of 5.0 C after 25 cycles). This superior electrochemical performance of the electrode can be attributed to the various aspects, such as,(1) the existence of carbon matrix, which acts as a flexible buffer to accommodate the volume changes during Li~+ion insertion/deinsertion and facilitates the fast Li~+and electron transfer and(2) the anchoring of Co_3O_4 nanoparticles within the carbon matrix prevents particles agglomeration.     

Microstructure and magnetic properties of Co/Al2O3 nanocomposite powders

Nanocomposite powders of magnetic cobalt nanoparticles dispersed by nonmagnetic Al₂O₃ particles have been prepared by planetary ball milling. Ball milling of the CoO and Al mixture powder after a certain milling duration reduces CoO to (fcc and hcp) Co completely and oxidizes Al to -Al₂O₃ simultaneously. The average grain sizes of the nanocomposite powders are 19 nm for Co and 28 nm for -Al₂O₃ after the completion of the reduction reaction. By direct ball milling of the mixture of Co and Al₂O₃, the allotropic phase transformation of Co was observed and the average grain size of Co is reduced to 5 nm. For both the samples of the mechanochemical series and the direct milling series, the saturation magnetizations of the nanocomposite powders decrease with decreasing average grain size of Co. This may be due to the enhancement of the interface effects and the increase of the superparamagnetic particles with decreasing Co grain size. The coercivities of the Co/Al₂O₃ nanocomposite powders increase up to 380 Oe. The increasing grain boundaries with decreasing Co grain size result in the domain wall pinning which predicts the coercivity enhancement. In addition to the grain size effects, the reduction of the particle size toward the size region of single domain also contributes to the increase of coercivity.     

Preparation and properties of a γ-Al2O3 washcoat deposited on a ceramic honeycomb

Washcoat deposited on ceramic honeycomb was prepared using pseudoboehmite, the CeO₂–ZrO₂–La₂O₃ solid solution, pore enlarger and other additives. The microstructures and surface performances of washcoat/honeycomb were investigated by SEM, BET surface area, XRD, ultrasonic vibration and hot shock simulation. The results show that the performance and loading of washcoat are affected obviously by the properties of slurry gel, such as the apparent viscosity, solid content, particle size and its distribution. When the apparent viscosity of slurry is lower, the gel with a narrow particle size distribution and finer particles can be obtained, with which the coating having an excellent performance can be prepared. Adding a small quantity of the CeO₂–ZrO₂–La₂O₃ solid solution can promote the thermal stability of washcoat, such as, after calcined at 1000 °C for 5 h the sample exhibits mainly the γ-Al₂O₃ phases and the θ-Al₂O₃ -Al₂O₃ and κ-Al₂O₃ phases have not been detected in the XRD spectra. It is found also that the washcoat prepared has excellent properties of the vibration-resistant, heat-resistant and its BET surface area reaches 50 m²/g.     

Effects of noble metal addition on microstructure and thermoelectric properties of NaxCo2O4

The synthesis of Na_xCo₂O₄/Ag and Na_xCo₂O₄/Au composites was tried by mechanical milling and subsequent sintering. Ag and Au particles were added to the Na_xCo₂O₄ powder prior to the mechanical milling. The microstructure and thermoelectric properties of the Na_xCo₂O₄/Au composite were compared to those of the Na_xCo₂O₄/Ag composite and the Na_xCo₂O₄ single phase, and the effects of the Ag and Au addition on the thermoelectric performance of Na_xCo₂O₄ were discussed. Au particles around 2 μm or smaller in size, which were significantly smaller than Ag particles around 10 μm in size, were dispersed in the Na_xCo₂O₄ matrix. The Seebeck coefficient and the electrical resistivity of Na_xCo₂O₄ were slightly enhanced and significantly reduced by these noble metals addition, resulting in the large power factor of these composites. On the other hand, the Na_xCo₂O₄/Au composite showed the electrical resistivity larger than that of the Na_xCo₂O₄/Ag composite. Ag and Au addition markedly increased the thermal conductivity, and the dimensionless figure of merit of Na_xCo₂O₄ could not be improved by these noble metals addition.     

Thermodynamic properties and phase diagrams of the binary systems B2O3–Ga2O3, B2O3–Al2O3 and B2O3–In2O3

We calculated the binary phase diagrams B₂O₃–Ga₂O₃, B₂O₃–In₂O₃ and B₂O₃–Al₂O₃, and the Gibbs energy of formation of the binary compounds, using experimental liquidus data. The B₂O₃–Ga₂O₃ system is of industrial importance, because liquid B₂O₃, in which Ga₂O₃ is not very soluble, is used to protect GaAs during growth of single crystals of GaAs. During recovery of noble metals B₂O₃ is added to slags containing Al₂O₃ to lower the melting point and the viscosity. The B₂O₃–In₂O₃ system is of much less importance to industry. In all three systems we have a liquid miscibility gap, and also solid binary compounds, none of which melt congruently. The miscibility gaps are not surprising, because even in the B₂O₃–Bi₂O₃ system where four congruently melting compounds are present, a liquid miscibility gap exists close to B₂O₃.     

The molybdenum diphosphate Mo1.3O(P2O7), containing Mo2 and Mo3 clusters

A novel molybdenum diphosphate, Mo_1.3O(P₂O₇), was obtained by electrochemical lithium deintercalation. The diphosphate crystallises in space group I2/a with the lattice parameters a=22.88(1), b=22.94(2), c=4.832(1) Å, γ=90.36°, Z=8. Its original framework is built up from MoO₆ octahedra, P₂O₇ groups and also from MoO₄, Mo₂O₄ and Mo₃O₈ units containing Mo₂ and Mo₃ clusters. These polyhedra delimit large octagonal and z-shaped tunnels running along c, in which the inserted cations may be located.     

TA2/ Co13Cr28Cu31Ni28/ Q235脉冲TIG焊接头组织与性能

针对钢与钛之间因物化性能差异大,焊接过程易产生大量金属间化合物而难以实现可靠连接的问题,依据焊缝金属固溶高熵化思路,选用Co₁₃Cr₂₈Cu₃₁Ni₂₈高熵合金作为中间过渡层对TA2钛和Q235钢进行脉冲钨极氩弧焊,并对Co₁₃Cr₂₈Cu₃₁Ni₂₈高熵合金及接头的组织和性能进行分析研究. 结果表明,Co₁₃Cr₂₈Cu₃₁Ni₂₈主要是双相面心立方结构,分别为富Cu的晶间和晶内面心立方结构,强度和塑性良好;焊接接头两部分焊缝均成形良好,无气孔、裂纹等缺陷,焊缝组织均为简单的固溶体结构,Q235侧焊缝主要为面心立方结构相,TA2侧焊缝主要由简单的体心立方结构和面心立方结构相构成,以体心立方结构相为主;焊接接头抗拉强度为224 MPa,在TA2侧靠近高熵合金的熔合线处断裂,主要由于生成了脆性的Cr₃O₈,断口有较多韧窝和一部分解理面,为混合断裂,表现出一定的韧性断裂特征.     

Improvement in hydrogen sorption properties of Mg by reactive mechanical grinding with Cr2O3, Al2O3 and CeO2

We tried to improve the hydrogen sorption properties of Mg by mechanical grinding under H₂ (reactive mechanical grinding) with oxides Cr₂O₃, Al₂O₃ and CeO₂. The hydriding rates of Mg are reportedly controlled by the diffusion of hydrogen through a growing Mg hydride layer. The added oxides can help pulverization of Mg during mechanical grinding. A part of Mg is transformed into MgH₂ during reactive mechanical grinding. The Mg+10wt.%Cr₂O₃ powder has the largest transformed fraction 0.215, followed in order by Mg+10wt.%CeO₂ and Mg+10wt.%Al₂O₃. The Mg+10wt.%Cr₂O₃ powder has the largest hydriding rates at the first and fifth hydriding cycle, followed in order by Mg+10wt.%Al₂O₃ and Mg+10wt.%CeO₂. Mg+10wt.%Cr₂O₃ absorbs 5.87wt.% H at 573 K, 11 bar H₂ during 60 min at the first cycle. The Mg+10wt.%Cr₂O₃ powder has the largest dehydriding rates at the first and fifth dehydriding cycle, followed by Mg+10wt.%CeO₂ and Mg+10wt.%Al₂O₃. It desorbs 4.44 wt.% H at 573 K, 0.5 bar H₂ during 60 min at the first cycle. All the samples absorb and desorb less hydrogen at the fifth cycle than at the first cycle. It is considered that this results from the agglomeration of the particles during hydriding–dehydriding cycling. The average particle sizes of the as-milled and cycled powders increase in the order of Mg+10wt.%Cr₂O₃, Mg+10wt.%Al₂O₃ and Mg+10wt.%CeO₂. The quantities of hydrogen absorbed or desorbed for 1 h for the first and fifth cycles decrease in the order of Mg+10wt.%Cr₂O₃, Mg+10wt.%Al₂O₃ and Mg+10wt.%CeO₂. The quantities of absorbed or desorbed hydrogen increase as the average particle sizes decrease. As the particle size decreases, the diffusion distance shortens. This leads to the larger hydriding and dehydriding rates. The Cr₂O₃ in the Mg+10wt.%Cr₂O₃ powder is reduced after hydriding–dehydriding cycling. The much larger chemical affinity of Mg than Cr for oxygen leads to a reduction of Cr₂O₃ after cycling.     

Synthesis and properties of Ba3NaRu2O9−δ and Ba3(Na, R)Ru2O9−δ (R=rare earth) crystals

Crystals of Ba₃NaRu₂O_9−δ (δ≈0.5) and Ba₃(Na, R)Ru₂O_9−δ (R=Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb) were grown by an electrochemical method, and their crystallographic, magnetic, and electric properties were studied. All crystals have a hexagonal structure of space group P6₃mmc. Ba₃NaRu₂O_9−δ and Ba₃(Na, R)Ru₂O_9−δ (except Ce) have a negative asymptotic Curie temperature suggesting the existence of an antiferromagnetic order; however, they are paramagnetic at temperatures above 1.7 K. Ba₃NaRu₂O_9−δ has an effective magnetic moment P_eff of 0.91 μ_B, while P_eff of Ba₃(Na, R)Ru₂O_9−δ (except Ce) reflects the large free-ion moment of the rare earth ions. Ba₃(Na, Ce)Ru₂O_9−δ shows peculiar magnetic behavior that differs from the magnetism of other Ba₃(Na, R)Ru₂O_9−δ crystals. The resistivity of all crystals exhibits an activation-type temperature dependence with an activation energy in the range of 0.10.2 eV.     

Subsolidus phase relations in the ZnO–MoO3–B2O3, ZnO–MoO3–WO3 and ZnO–WO3–B2O3 ternary systems

The subsolidus phase relations in the ZnO–MoO₃–B₂O₃, ZnO–MoO₃–WO₃ and ZnO–WO₃–B₂O₃ ternary systems have been investigated by the means of X-ray powder diffraction (XRD). There is no ternary compound in all the systems. There are five binary compounds and five tie lines in the ZnO–MoO₃–B₂O₃ system. This system can be divided into six 3-phase regions. There are three binary compounds and three tie lines in the ZnO–MoO₃–WO₃ system. This system can be divided into four 3-phase regions. There are four binary compounds and four tie lines in the ZnO–WO₃–B₂O₃ system. This system can be divided into five 3-phase regions. The possible component regions for ZnO single crystal flux growth were discussed. The phase diagram of Zn₃B₂O₆–ZnWO₄ pseudo-binary system has been constructed, and the result reveals this system is eutectic system. The eutectic temperature is 1007 °C and eutectic point component is 70 mol% Zn₃B₂O₆.     

Effects of modification on performance of natural graphite coated by SiO2 for anode of lithium ion batteries

A stable silicon dioxide film was coated on the surface of natural graphite anode by sol-gel method with Si（OCH2CH3）4, and effects of modification on performance of natural graphite were investigated. The structure and properties of graphite samples were determined by X-ray diffi＇actometry（XRD）, scanning electron microscopy（SEM）, energy-dispersive X-ray spectroscopy（EDS） and electrochemical measurements. The modified graphite shows mainly the layer structure, and silicon dioxide film is amorphous. Compared with the pure natural graphite, the modified graphite exhibits the higher specific capacity of 366 mA-h/g. After 40 charge-discharge cycles, the capacity retention ratio of the modified graphite reaches 99.55%, while that of natural graphite is only 83.04%. The results indicate that the surface modification of natural graphite by SiO2 is effective for improving the electrochemical performance of the natural graphite anode for lithium ion batteries.