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.     

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（1.5nm）.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）.     

Design of layered-stacking graphene assemblies as advanced electrodes for supercapacitors

Graphene is a competitive electrode material for supercapacitors due to its unique two-dimensional structure, large surface area, high conductivity, and good physicochemical stability. However, random agglomeration and restacking of graphene sheets result in a reduced surface area and a loose structure with low density, which severely restricts the application for high gravimetric/volumetric energy density devices. Rational design of the layered-stacking structure of graphene assemblies can effectively prevent the restacking of graphene sheets, construct efficient ion transport channels, and improve spatial utilization, demonstrating the huge potential for developing advanced electrode materials. Herein, from the aspect of improving the electrochemical kinetics through designing efficient electron and ion transport paths, we first highlight the advantages of layered-stacking graphene assemblies, describe some common routes for preparing graphene building units, and then summarize the novel methods to design layered-stacking structures. A comprehensive review of the typical structure including nanocarbon pillared graphene, porous graphene blocks, and graphene ribbon films is provided with a focus on the mechanisms behind the performance improvements. Finally, critical challenges and some general ideas for future development are proposed, which may open up new opportunities for material chemistry and device innovation.     

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.     

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.     

Dry modification of electrode materials by roller vibration milling at room temperature

For the first time dry roller vibration milling at room temperature was used to prepare active carbon (AC) nano-particles and to modify MnO2 powder as electrode materials.In 30min AC was milled to a mean particle size of 30-50nm with increased crystallinity and higher specific surface area,predominantly mesoporous and with improved pore diameter distribution.Then,AC nano-particles were incorporated with MnO2 or bismuth-doped MnO2 nano-particles synthesized by sol-gel methods to prepare nano-composite electrode materials for studying their electrochemical performance.The AC nano-particles combined with 10 wt.% bismuth-doped MnO2 nano-particles were found to possess excellent electrochemical property with specific capacitance up to 308 F/g and without obvious attenuation with increasing current.Our method seems to open a new way to improve AC based electrode materials used for clean energy such as super capacitors.     

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).     

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.     

SYNTHESIS OF MESOPOROUS TiO_2 MATERIALS WITH HIGH SPECIFIC AREA USING INORGANIC ACIDS AS CATALYSTS

This paper presents a synthesis process for preparing mesoporous titanium dioxide materials in the absence of any templates and using inorganic acids as catalysts. Tetrabutyl titanate was used as the precursor at ambient temperature, and four different inorganic acids, i.e., hydrochloric, nitric, sulfuric and phosphoric, were used as catalysts. The as-prepared mesoporous TiO2 materials were characterized by SEM, XRD and nitrogen adsorption/desorption measurements. The influences of different inorganic acids on the properties of TiO2 were discussed and compared in details. Experiments showed that the inorganic acids have significant effects on the surface area, pore volume, pore size, and pore size distribution of the products. The mesoporous TiO2 materials catalyzed by phosphoric acid exhibited the largest specific surface area and largest pore volume with narrow pore size distribution. Vacuum and infrared drying methods tested in the process were found to have subtle impact on the structure of the TiO2 materials prepared.     

Dry modification of electrode materials by roller vibration milling at room temperature

For the first time dry roller vibration milling at room temperature was used to prepare active carbon （AC） nano-particles and to modify MnO2 powder as electrode materials. In 30 min AC was milled to a mean particle size of 30-50 nm with increased crystallinity and higher specific surface area, predominantly mesoporous and with improved pore diameter distribution. Then, AC nano-particles were incorporated with MnO2 or bismuth-doped MnO2 nano-particles synthesized by sol-gel methods to prepare nano-composite electrode materials for studying their electrochemical performance. The AC nano-particles combined with 10 wt.% bismuth-doped MnO2 nano-particles were found to possess excellent electrochemical property with specific capacitance up to 308 F/g and without obvious attenuation with increasing current. Our method seems to ooen a new way to imorove AC based electrode materials used for clean energy such as suner capacitors.     

Microwave-hydrothermal preparation of a graphene/hierarchy structure MnO2 composite for a supercapacitor

Graphene/hierarchy structure manganese dioxide （GN/MnO2） composites were synthesized using a simple microwave-hydrothermal method. The properties of the prepared composites were analyzed using field emission scanning electron microscopy （FE-SEM）, X-ray diffraction （XRD）, transmission electron microscopy （TEM）, and X-ray photoelectron spectroscopy （XPS） measurements. The electrochemical performances of the composites were analyzed using cyclic voltammetry, electrochemical impedance spectrometry （EIS）, and chronopotentiometry. The results showed that GN/MnO2 （10 wt% graphene） displayed a specific capacitance of 244 F/g at a current density of 100 mA/g. An excellent cyclic stability was obtained with a capacity retention of approximately 94.3% after 500 cycles in a 1 mol/L Li2SO4 solution. The improved electrochemical performance is attributed to the hierarchy structure of the manganese dioxide, which can enlarge the interface between the active materials and the electrolyte. The prepa- ration route provides a new approach for hierarchy structure graphene composites; this work could be readily extended to the preparation of other graphene-based composites with different structures for use in energy storage devices.     

钛合金表面自润滑复合耐磨结构的制备及其摩擦性能研究

本文中采用激光微加工法在TC4钛合金表面制备了不同形貌与分布密度的微观织构,将表面织构、热氧化膜与PTFE润滑薄膜相复合制备了自润滑复合耐磨结构,同时考察了滑动条件下织构形貌及织构密度对这一复合结构摩擦磨损性能的影响.结果表明：与未织构面的润滑薄膜相比,织构面薄膜的结合力明显增大,表面织构与润滑薄膜的结合显著增强了材料的减摩抗磨性能.在最优的织构密度下,含有薄膜的织构化钛合金表面的磨损率可降低至1.5×10^-6 mm³/(N·m),较未织构面润滑薄膜的磨损率降低了99.3%.而将经热氧化的织构表面与润滑薄膜的结合则进一步提升了材料的耐磨性,热氧化织构面润滑薄膜的磨损率最低可达8.0×10^-7 mm³/(N·m),与未热氧化的织构面润滑薄膜相比,磨损率降低了46.1%.在相同的织构间距条件下,线型热氧化织构面显示出低而稳定的摩擦系数与极低的磨损量,这主要得益于高密度微织构对润滑介质的有效补充以及高硬度热氧化膜的耐磨性起到了协同减摩抗磨的作用.     

Preparation of high-purity monodisperse silica microspheres by the sol-gel method coupled with polymerization-induced colloid aggregation

Ultra-pure mesoporous silica microspheres with good monodispersity were synthesized in two steps:nanometer-sized silica sol was produced by the sol-gel process,then micrometer-sized silica microspheres were synthesized by polymerization-induced colloid aggregation of the silica sol.The total metal content of the microspheres was extremely low,which eliminated the tailing of chromatographic peaks by chelating reagents.The pore structure of the silica microspheres could be controlled by altering the sol-gel conditions.The silica microsphere particle size could be adjusted by using different polymerizationinduced colloid aggregation conditions.     

石英添加量对搪瓷涂层微观结构及摩擦磨损性能的影响

采用一次浸搪法制备石英添加量为0%、4%、8%和12%的搪瓷涂层,通过HSR-2M型高速往复摩擦试验机测试涂层摩擦学性能,SEM和EDS分别表征涂层微观组织和磨损形貌,并分析磨损机理. 结果表明:搪瓷涂层中石英添加质量分数为0%和4%时,涂层气孔率大、气孔密度低,摩擦时形成的微裂纹易沿着气孔间最短距离方向扩展,硬质磨屑转移至摩擦对偶表面而使涂层磨痕底部形成尖锐的凹槽,磨损形式主要为磨粒磨损和脆性断裂. 而石英添加质量分数为8%和12%的涂层气孔率小、气孔密度高,其中8%添加量涂层的孔径分布更加均匀,磨损率及磨痕深度仅为未添加涂层的1/3. 摩擦过程中孔径均匀的小尺寸气孔增大了裂纹扩展时所需的能量势垒而阻碍裂纹扩展,磨屑被气孔拦截后在磨损表面形成密实的堆积层,避免了摩擦对偶与涂层的直接接触而起到减摩作用,磨损形式主要为磨粒磨损.      

工作电压对N36锆合金表面微弧氧化涂层磨蚀性能的影响

通过微弧氧化(MAO)设备在锆(Zr)合金表面制备氧化陶瓷涂层. 研究工作电压对Zr合金表面MAO涂层形貌、硬度、粗糙度、元素分布和相结构的影响. 分析工作电压对Zr合金表面MAO涂层腐蚀和磨蚀性能的影响. 结果表明:MAO涂层表面具有典型的多孔和火山熔融特征,主要由m-ZrO₂和t-ZrO₂相组成. MAO涂层的粗糙度比基体高,且在电压为340 V时的粗糙度最高,达到1.36 μm. MAO涂层可分为内层致密层和外层多孔层,涂层厚度随着工作电压的增加而增加,厚度为5~9 μm. 电压为260 V的MAO涂层的结合强度最高,达到44.3 N. MAO涂层相比较于基体具有更好的耐腐蚀性能,电压为260 V的MAO涂层具有最高的自腐蚀电位(?0.205 V)和最低的腐蚀电流密度(6.24×10?9 A/cm2). 这是因为电压为260 V的MAO涂层具有最致密的结构,而内层致密层可以阻碍腐蚀液进入基体. MAO涂层的主要磨损机理为磨粒磨损和氧化磨损. 工作电压为260 V的MAO涂层的磨损率仅为Zr合金基体的1/4.      

织构化表面NbSe2涂层的真空载流摩擦学行为

针对航天器滑动电接触部件特殊的真空载流服役要求,利用建立的真空载流摩擦试验平台,探索铜基材织构化表面喷涂NbSe₂涂层作为空间新型导电润滑材料的可能性.研究条状和网状不同织构以及各自在不同织构密度条件下喷涂NbSe₂涂层的真空载流摩擦学性能和影响作用规律;对比现役电镀金涂层,探讨其在真空载流条件下摩擦学和电接触行为优势.结果表明：网格状较条状织构表面喷涂NbSe₂涂层的载流摩擦学性能更好,而且随织构密度的增加,减摩耐磨性能得到提高.织构间距为200μm的网格状织构表面喷涂的NbSe₂涂层展现出最佳的真空载流摩擦学性能.相较于现役的金电镀层,其在真空载流摩擦条件下展现出更加优异的摩擦学和电接触性能,摩擦系数由0.25降至0.05,接触电压与现役材料处于同一量级,电噪音波动明显改善,由0.09V降至0.04V.     

Effect of pore size distribution in bidisperse wick on heat transfer in a loop heat pipe

The purpose of this article is to experimentally investigate the effect of different pore size distributions in bidisperse wicks upon the heat transfer performance in a LHP. Three bidisperse wicks and one monoporous wick were tested in a loop heat pipe. The pore size distributions of the bidisperse wicks were measured, and the results reflected the three different large/small pore size ratios. The experiments showed that the maximum heat load of the monoporous wick reached about 400 W; and the three bidisperse wicks showed improvements on the maximum heat load up to 570 W. For the monoporous wick, the evaporator heat transfer coefficients of 10 kW/m² K and total thermal resistance of 0.19°C/W were achieved at a high heat load of 400 W. For the better bidisperse wick, the evaporator heat transfer coefficients could attain about 23 kW/m² K and total thermal resistance of 0.13°C/W. The results also indicated that a smaller cluster size in a bidisperse structure created a small pore size ratio. It was also found that the bidisperse wick with smaller clusters had a better enhancement in terms of the evaporator heat transfer coefficient.     

Electro-chemo-mechanical analysis of the effect of bending deformation on the interface of flexible solid-state battery

Flexible solid-state battery has several unique characteristics including high flexibility, easy portability, and high safety, which may have broad application prospects in new technology products such as rollup displays, power implantable medical devices, and wearable equipments. The interfacial mechanical and electrochemical problems caused by bending deformation, resulting in the battery damage and failure, are particularly interesting. Herein, a fully coupled electro-chemo-mechanical model i...     

离子束混合铝／铁双层膜表面改性

目前，有关离子束混合层的摩擦磨损性能及其电化学腐蚀等方面内容文献报道还很少见，研究都还不够深入系统。因此，对Ａｒ＾＋离子束混合３１６不锈钢基体上的Ａｌ／Ｆｅ双层膜的摩擦学行为及其电化学性能等进行了试验研究，结果表明，混合层的显微硬度比基体的高２５％，摩擦系数也大幅度降低，且其耐磨性能良好，混合试样的电化学性能表现明显的贵金属特征，在此基础上，还利用俄歇电子能谱仪，透射电子显微镜，扫描电子显微镜和掠     

Strain Evolution in Lithium Manganese Oxide Electrodes

Lithium manganese oxide, LiMn₂O₄ (LMO) is a promising cathode material, but is hampered by significant capacity fade due to instability of the electrode-electrolyte interface, manganese dissolution into the electrolyte and subsequent mechanical degradation of the electrode. In this work, electrochemically-induced strains in composite LMO electrodes are measured using the digital image correlation (DIC) technique and compared with electrochemical impedance spectroscopy (EIS) measurements of surface resistance for different scan rates. Distinct, irreversible strain variations are observed during the first delithiation cycle. The changes in strain and surface resistance are highly sensitive to the electrochemical changes occurring during the first cycle and correlate with prior reports of the removal of the native surface layer and the formation of cathode-electrolyte interface layer on the electrode surface. A large capacity fade is observed with increasing cycle number at high scan rates. Interestingly, the total capacity fade scales proportionately to the strain generated after each lithiation and delithiation cycle. The simultaneous reduction in capacity and strain is attributed to chemo-mechanical degradation of the electrode. The in situ strain measurements provide new insight into the electrochemical-induced volumetric changes in LMO electrodes with progressing cycling and may provide guidance for materials-based strategies to reduce strain and capacity fade.