Mesoporous composite of LiFePO4 and carbon microspheres as positive-electrode materials for lithium-ion batteries

Mesoporous LiFePO₄/C microspheres consisting of LiFePO₄ nanoparticles are successfully fabricated by an eco-friendly hydrothermal approach combined with high-temperature calcinations using cost-effective LiOH and Fe³⁺ salts as raw materials. In this strategy, pure mesoporous LiFePO₄ microspheres, which are composed of LiFePO₄ nanoparticles, were uniformly coated with carbon (∼1.5 nm). Benefiting from this unique architecture, these mesoporous LiFePO₄/C microspheres can be closely packed, having high tap density. The initial discharge capacity of LiFePO₄/C microspheres as positive-electrode materials for lithium-ion batteries could reach 165.3 mAh/g at 0.1 C rate, which is notably close to the theoretical capacity of LiFePO₄ due to the large BET surface area, which provides for a large electrochemically available surface for the active material and electrolyte. The material also exhibits high rate capability (∼100 mAh/g at 8 C) and good cycling stability (capacity retention of 92.2% after 400 cycles at 8 C rate).     

Open-pore LiFePO_4/C microspheres with high volumetric energy density for lithium ion batteries

LiFePO_4/C microspheres with different surface morphologies and porosities were prepared from different carbon sources.The effects of the surface morphology and pore structure of the microspheres on their electrochemical properties and electrode density were investigated.The electrochemical performance and electrode density depended on the morphology and pore structure of the LiFePO_4/C microspheres.Open-pore LiFePO_4/C microspheres with rough surfaces exhibited good adhesion with current collectors and a high electrode density(2.6g/cm~3).They also exhibited high performance in a half cell and full battery with a high volumetric energy density.     

Solid-state synthesis of Li[Li_(0.2)Mn_(0.56)Ni_(0.16)Co_(0.08)]O_2 cathode materials for lithium-ion batteries

Layered Li|Li_(0.2)Mn_(0.56)Ni_(0.16)Co_(0.08]O_2 cathode materials were synthesized via a solid-state reaction for Liion batteries,in which lithium hydroxide monohydrate,manganese dioxide,nickel monoxide,and cobalt monoxide were employed as metal precursors.To uncover the relationship between the structure and electrochemical properties of the materials,synthesis conditions such as calcination temperature and time as well as quenching methods were investigated.For the synthesized Li[Li_(0.2)Mn_(0.56)Ni_(0.16)Co_(0.08)]O_2materials,the metal components were found to be in the form of Mn~(4+),Ni~(2+),and Co~(3+),and their molar ratio was in good agreement with stoichiometric ratio of 0.56:0.16:0.08.Among them,the one synthesized at 800 C for 12 h and subsequently quenched in air showed the best electrochemical performances,which had an initial discharge specific capacity and coulombic efficiency of 265.6 mAh/g and 84.0%,respectively,and when cycled at 0.5,1,and 2C,the corresponding discharge specific capacities were 237.3,212.6.and 178.6 mAh/g,respectively.After recovered to 0.1 C rate,the discharge specific capacity became259.5 mAh/g and the capacity loss was only 2.3% of the initial value at 0.1 C.This work suggests that the solid-state synthesis route is easy for preparing high performance Li[Li_(0.2)Mn_(0.56)Ni_(0.16)Co_(0.08)]O_2 cathode materials for Li-ion batteries.     

Si-induced insertion of Li into SiC to form Li-rich SiC twin crystal

The energy density of Li-ion batteries is closely related to the capacity and average voltage of cathode materials. Unfortunately, current cathode materials either have low capacity or voltage, which limits the development of high-energy-density Li-ion batteries. This has given challenge to many attempts to develop new cathode materials with high capacity and voltage. In this study, we find that Li easily inserts into the (111) plane of SiC in the presence of Si, and a well-organized Li-rich SiC twin crystal is formed. Ultraviolet–visible diffuse reflectance spectra and electrochemical test results suggest that this Li-rich SiC twin crystal possesses the band gap energy of 3.5 eV and charging capacity of 1979 mAh/g at the current density of 200 mA/g, making it a promising candidate for the cathode material in high-capacity Li-ion batteries. X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy results reveal that Si-induced Li insertion contributes to the changes in the surface species and structure of pristine SiC. These findings suggest that the Li-rich SiC twin crystal raises new possibilities for the development of high-capacity cathode materials and merits further investigation to expand its application scope.     

Preparation and Li^＋ storage properties of hierarchical hollow porous carbon spheres

Hollow ordered porous carbon spheres （HOPCS） with a hierarchical structure were prepared by templating with hollow ordered mesoporous silica spheres （HOMSS）. Scanning electron microscopy （SEM） and transmission electron microscopy （TEM） showed that HOPCS exhibited a spherical hollow morphology. High-resolution TEM, small angle X-ray diffraction （SAXRD） and N2 sorption measurements confirmed that HOPCS inversely replicated the unconnected hexagonal-stacked pore structure of HOMSS, and possessed ordered porosity. HOPCS exhibited a higher storage capacity for Li^＋ ion battery （LIB） of 527.6 mA h/g, and good cycling performance. A large capacity loss during the first discharge-charge cycle was found attributed to the high content of micropores. The cycling performance was derived from the hierarchical structure.     

Electrochemical performance of polygonized carbon nanofibers as anode materials for lithium-ion batteries

Carbon nanofibers with a polygonal cross section (P-CNFs) synthesized using a catalytic chemical vapor deposition (CCVD) technology have been investigated for potential applications in lithium batteries as anode materials. P-CNFs exhibit excellent high-rate capabilities. At a current density as high as 3.7 and 7.4 A/g, P-CNFs can still deliver a reversible capacity of 198.4 and 158.2 mAh/g, respectively. To improve their first coulombic efficiency, carbon-coated P-CNFs were prepared through thermal vapor deposition (TVD) of benzene at 900 °C. The electrochemical results demonstrate that appropriate amount of carbon coating can improve the first coulombic efficiency, the cycling stability and the rate performance of P-CNFs. After carbon coating, P-CNFs gain a weight increase approximately by 103 wt%, with its first coulombic efficiency increasing from 63.1 to 78.4%, and deliver a reversible capacity of 197.4 mAh/g at a current density of 3.7 A/g. After dozens of cycles, there is no significant capacity degradation at both low and high current densities.     

Open-pore LiFePO4/C microspheres with high volumetric energy density for lithium ion batteries

LiFePO₄/C microspheres with different surface morphologies and porosities were prepared from different carbon sources. The effects of the surface morphology and pore structure of the microspheres on their electrochemical properties and electrode density were investigated. The electrochemical performance and electrode density depended on the morphology and pore structure of the LiFePO₄/C microspheres. Open-pore LiFePO₄/C microspheres with rough surfaces exhibited good adhesion with current collectors and a high electrode density (2.6 g/cm³). They also exhibited high performance in a half cell and full battery with a high volumetric energy density.     

Solid-state synthesis of Li[Li0.2Mn0.56Ni0.16Co0.08]O2 cathode materials for lithium-ion batteries

Layered Li[Li_0.2Mn_0.56Ni_0.16Co_0.08]O₂ cathode materials were synthesized via a solid-state reaction for Li-ion batteries, in which lithium hydroxide monohydrate, manganese dioxide, nickel monoxide, and cobalt monoxide were employed as metal precursors. To uncover the relationship between the structure and electrochemical properties of the materials, synthesis conditions such as calcination temperature and time as well as quenching methods were investigated. For the synthesized Li[Li_0.2Mn_0.56Ni_0.16Co_0.08]O₂ materials, the metal components were found to be in the form of Mn⁴⁺, Ni²⁺, and Co³⁺, and their molar ratio was in good agreement with stoichiometric ratio of 0.56:0.16:0.08. Among them, the one synthesized at 800 °C for 12 h and subsequently quenched in air showed the best electrochemical performances, which had an initial discharge specific capacity and coulombic efficiency of 265.6 mAh/g and 84.0%, respectively, and when cycled at 0.5, 1, and 2 C, the corresponding discharge specific capacities were 237.3, 212.6, and 178.6 mAh/g, respectively. After recovered to 0.1 C rate, the discharge specific capacity became 259.5 mAh/g and the capacity loss was only 2.3% of the initial value at 0.1 C. This work suggests that the solid-state synthesis route is easy for preparing high performance Li[Li_0.2Mn_0.56Ni_0.16Co_0.08]O₂ cathode materials for Li-ion batteries.     

Preparation and electrochemical performance of carbon-coated LiFePO4/LiMnPO4-positive material for a Li-ion battery

Lithium iron phosphate (LiFePO₄)/lithium manganese phosphate (LiMnPO₄)-positive material was successfully prepared through ball milling and high-temperature sintering using manganese acetate, lithium hydroxide, ammonium dihydrogen phosphate, and ferrous oxalate as raw materials. The as-prepared samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, a constant current charge–discharge test, cyclic voltammetry, and electrochemical impedance spectroscopy. The effects of lithium iron phosphate coating were also discussed. Because of its special core–shell structure, the as-prepared LiMn_0.7Fe_0.3PO₄–LiFePO₄–C exhibits excellent electrochemical performance. The discharge capacity reached 136.6 mAh/g and the specific discharge energy reached 506.9 Wh/kg at a rate of 0.1 C.     

Lithium-storage properties of SiO2 nanotubes@C using carbon nanotubes as templates

Silica-based anode material is the most concerned material at present, which has the advantages of good cycle stability, high theoretical specific capacity and abundant reserves. However, silica suffers from inherent low conductivity, severe volume expansion effect and low initial coulombic efficiency, which limits its application in lithium-ion batteries. Nanotubes structure can mitigate the volume expansion during lithiation/delithiation. In this article, silica nanotubes (SNTs) were prepared using carbon nanotubes (CNTs) as a template, and then the uniform carbon layer was coated on their surface by carbonization of citric acid. The hollow structure of nanotubes provides more sites for the insertion of Li⁺ during lithiation and additional channels for Li⁺ migration in the cycles, which improves the electrochemical performance. Conductivity can be enhanced by coating carbon layer. The specific capacity of the composite material is about 650 mAh g⁻¹ at 0.1 A g⁻¹ after 100 cycles. With a specific capacity of 400 mAh g⁻¹ even at 1 A g⁻¹ after 100 cycles. The silica-based material is a competitive anode material for lithium-ion batteries.     

Highly dispersed Mn2O3 microspheres: Facile solvothermal synthesis and their application as Li-ion battery anodes

Nanostructured transition metal oxides are promising alternative anodes for lithium ion batteries. Li-ion storage performance is expected to improve if high packing density energy particles are available. Herein, Mn₂O₃ microspheres with a ca. 18 μm diameter and a tapped density of 1.33 g/cm³ were synthesized by a facile solvothermal–thermal coversion route. Spherical MnCO₃ precursors were obtained through solvothermal treatment and they decomposed and converted into Mn₂O₃ microspheres at an annealing temperature of 700 °C. The Mn₂O₃ microspheres consisted of Mn₂O₃ nanoparticles with an average 40 nm diameter. These porous Mn₂O₃ microspheres allow good electrolyte penetration and provide an ion buffer reservoir to ensure a constant electrolyte supply. The Mn₂O₃ microspheres have reversible capacities of 590 and 320 mAh/g at 50 and 400 mA/g, respectively. We thus report an efficient route for the fabrication of energy particles for advanced energy storage.     

Microwave-assisted polyol synthesis of LiMnPO4/C and its use as a cathode material in lithium-ion batteries

We synthesized LiMnPO₄/C with an ordered olivine structure by using a microwave-assisted polyol process in 2:15 (v/v) water–diethylene glycol mixed solvents at 130 °C for 30 min. We also studied how three surfactants—hexadecyltrimethylammonium bromide, polyvinylpyrrolidone k30 (PVPk30), and polyvinylpyrrolidone k90 (PVPk90)—affected the structure, morphology, and performance of the prepared samples, characterizing them by using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, charge/discharge tests, and electrochemical impedance spectroscopy. All the samples prepared with or without surfactant had orthorhombic structures with the Pnmb space group. Surfactant molecules may have acted as crystal-face inhibitors to adjust the oriented growth, morphology, and particle size of LiMnPO₄. The microwave effects could accelerate the reaction and nucleation rates of LiMnPO₄ at a lower reaction temperature. The LiMnPO₄/C sample prepared with PVPk30 exhibited a flaky structure coated with a carbon layer (∼2 nm thick), and it delivered a discharge capacity of 126 mAh/g with a capacity retention ratio of ∼99.9% after 50 cycles at 1C. Even at 5C, this sample still had a high discharge capacity of 110 mAh/g, demonstrating good rate performance and cycle performance. The improved performance of LiMnPO₄ likely came from its nanoflake structure and the thin carbon layer coating its LiMnPO₄ particles. Compared with the conventional polyol method, the microwave-assisted polyol method had a much lower reaction time.     

SYNTHESIS AND COATING OF ORDERED MESOPOROUS SILICA

1,3,5-trimethyl benzene (TMB) was used as organic swelling agent in O/W emulsions to template ultra-large mesoporous materials using the hydrothermal method. The silicas with well-defined mesopores and hydrothermally robust framework were characterized by X-ray diffraction, transmission electron microscopy and BET surface area analysis. The influence of the quantity of TMB during preparation was studied. It has been found that the TMB/CTAB ratio must be controlled for producing high pore volume materials. Polysulfone (PSU), as the usual extraction agent, was coated on the silicas with the solvent evaporation method to produce a solid separation medium. The adsorptivity and the surface area of the coated MCM were determined: 10% PSU coated MCM adsorbed twice as much phenol as the uncoated material, reaching 0.5 mg/g silica. It was found that the surface area of the coated material decreased rapidly with an increase of the PSU Ioadina.     

Polymer nanoparticles with dendrimer-Ag shell and its application in catalysis

Polymer nanoparticles with dendrimer-Ag shell were prepared and their application in catalytic reduction of 4-nitrophenol (4-NP) was investigated. Cross-linked polystyrene (PS) microspheres were prepared through dispersion copolymerization of styrene, acrylic acid and crosslinking monomer 1, 2-divinylbenzene. PS microspheres with average size of 450 nm and narrow size distribution were used as support for the immobilization of dendrimer-Ag shell. The polyamidoamine (PAMAM) dendrimer shell was successively grafted onto the surface of PS microspheres through repetitive Michael addition reaction of methyl acrylate (MA) and amidation of the obtained esters with large excess of ethylenediamine (EDA). Silver nanoparticles were formed directly inside the PAMAM shell through reduction with NaBH₄. The resulting PS@PAMAM-Ag nanoparticles were packed in a stainless steel column and used successfully for catalytic reduction of 4-NP. This technique for packing catalytic polymer particles in a column could improve the efficiency of using the metal catalyst and the tedious separation in catalytic reaction.     

POROUS SILICA NANO-TUBE AS HOST FOR ENZYME IMMOBILIZATION

With their hollow morphology and large openings, the as-synthesized porous silica nano-tubes (NTPS), prepared through a sol-gel routine by using nano-sized needle-shaped CaCO3 particles as templates, were used as host for enzyme immobilization. Bioimmobilization study showed that enzyme molecules could not only be adsorbed on the external surface of NTPS but also entrapped in their inner hollow cores, leading to higher enzyme loading capacities of NTPS (more than 350 mg/g silica) in a shorter time, as compared to common porous silica (less than 50 mg/g) and most conventional mesoporous silica materials (less than 100 mg/g).     

Carbon combustion synthesis of lithium cobalt oxide as cathode material for lithium ion battery

Lithium cobalt oxide (LiCoO2) was synthesized by carbon combustion synthesis (CCS) using carbon as fuel. X-ray diffraction (XRD) and scanning electron microscope (SEM) measurements showed that carbon combustion led to the formation of layered structure of LiCoO2 and the particle size could be controlled by carbon content. For the LiCoO2 sample prepared at 800 ℃ for 2 h, at molar ratio of C/Co= 0.5, the particle-size distribution fell in the narrow range of 3-5 μm. Electrochemical tests indicated this LiCoO2 sample delivered an initial discharge capacity of 148 mAh/g with capacity retention rate higher than 97% after 10 cycles.     

Preparation and functionalization of mesoporous silica spheres as packing materials for HPLC

This paper presents the integrated results of a series of new methods for preparing mesoporous silica spheres as high-performance liquid chromatography （HPLC） packing materials. The separation performance of the mesoporous spheres materials has also been determined. Micrometer- sized silica spheres with uniform spherical morphologies and ordered mesostructures were first successfully synthesized by the method employing a water-soluble polymer-assisted assembly. Then the templates for getting ordered mesoporous materials with high-density silanol groups were removed by using hydrothermal oxidation. Finally the silica spheres were functionalized with C8 alkyl groups by surface modification under hydrothermal conditions. The resultant functionalized silica spheres were demonstrated to be excellent oacking materials for HPLC.     

Preparation and functionalization of mesoporous silica spheres as packing materials for HPLC

This paper presents the integrated results of a series of new methods for preparing mesoporous silica spheres as high-performance liquid chromatography (HPLC) packing materials. The separation performance of the mesoporous spheres materials has also been determined. Micrometersized silica spheres with uniform spherical morphologies and ordered mesostructures were first successfully synthesized by the method employing a water-soluble polymer-assisted assembly. Then the templates for getting ordered mesoporous materials with high-density silanol groups were removed by using hydrothermal oxidation. Finally the silica spheres were functionalized with C8 alkyl groups by surface modification under hydrothermal conditions. The resultant functionalized silica spheres were demonstrated to be excellent packing materials for HPLC.     

大尺寸Hopkinson压杆及其应用

本文介绍了国内最大尺寸的SHPB装置;讨论了在大尺寸SHPB装置上测量混凝土类材料动态力学性能将会出现的几个问题;采取了在入射杆的打击端加设波形整形器,在试件与杆件之间加设万向头及在试件上直接测量应变等新的实验技术及采用新的数据处理方法,提高了试验结果的精确度和可信度;简要介绍了利用ф100 SHPB装置对四种体积含量(0,2%,4%和6%)钢纤维高强混凝土进行三种应变率(10~20/s,35~45/s和75~85/s)的冲击压缩实验。实验结果表明,钢纤维高强混凝土具有较强的应变率效应,其破坏应力、峰值应变随应变率增加而显著增加,弹性模量也随应变率增加而增加。另外,钢纤维含量对混凝土具有增韧效应,随着钢纤维含量的增加,其韧性增大,脆性降低。     

微型Hopkinson杆技术

介绍了一种可对材料进行更高应变率动态性能实验的微型Hopkinson杆技术,对金属材料其应变可超过104 s-1。使用激光径向位移测试仪和与传统Hopkinson杆对比实验,对微型Hopkinson杆技术的有效性进行了验证。实验结果表明,微型Hopkinson杆确定的试样应变与激光径向位移测试的结果相当吻合;在低应变率范围内,与传统Hopkinson杆的实验结果有很好的一致性。从而证明了微型Hopkinson杆技术可进行应变率在104 s-1以上材料的动态力学性能实验。